Multifunctional chain shuttling agents

ABSTRACT

The invention generally relates to chain shuttling agents (CSAs), a process of preparing the CSAs, a composition comprising a CSA and a catalyst, a process of preparing the composition, a processes of preparing polyolefins, end functional polyolefins, and telechelic polyolefins with the composition, and the polyolefins, end functional polyolefins, and telechelic polyolefins prepared by the processes.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 12/845,023 filed on Jul. 28, 2010 and claims benefit from U.S.Provisional Patent Application No. 61/229,425, filed Jul. 29, 2009, theentire contents of which are hereby incorporated herein by reference.

FIELD OF THE INVENTION

The invention generally relates to chain shuttling agents (CSAs), aprocess of preparing the CSAs, a composition comprising a CSA and acatalyst, a process of preparing the composition, processes of preparingpolyolefins, end functional polyolefins, and telechelic polyolefins withthe composition, and the polyolefins, end functional polyolefins, andtelechelic polyolefins prepared by the processes.

BACKGROUND OF THE INVENTION Description of Related Art

Exchange or redistribution reactions of metal-ligand (e.g.,alkylaluminums, aryloxyaluminums, alkylzincs, alkoxyzincs, and the like)complexes containing or derived polymerization catalysts are known. Forexample, see Healy M. D. et al., Sterically crowded aryloxide compoundsof aluminum, Coordination Chemistry Reviews, 1994; 130(1-2):63-135; andStapleton R. A., et al., Olefin Polymerization, Organometallics, 2006;25(21):5083-5092.

Examples of telechelic polymers include polymeric chains containing ahydroxyl group at each chain end. Telechelic polymers can be used, forexample, as rocket fuel binders and as ingredients in coatings,sealants, and adhesives.

Telechelic polymers have been prepared by a number of methods. U.S. Pat.No. 5,247,023 mentions telechelic polymers prepared from hydrocarbonpolymers containing borane groups at chain ends or in polymer backbonesthereof. Such telechelic polymers have a statistical (i.e., essentiallyrandom) distribution of terminal functional groups.

Examples of polyolefin polymers include polyolefin homopolymers andpolyolefin block copolymers. Polyethylene (also known as polyethene orpoly(methylene)), polypropylene, and poly(ethylene alpha-olefin)copolymers are examples of polyolefins (also known as polyalkenes)widely used in industry. They are desirable for making, for example,containers, tubing, films and sheets for packaging, and syntheticlubricants.

Block copolymers often have superior properties to properties of randomcopolymers and polymer blends. Properties, characteristics and, hence,applications of block copolymers are influenced by, among other things,how the block copolymers are made and structure and characteristics ofcatalysts used to prepare them.

One method of preparing block copolymers is living polymerization.Domski et al. review block copolymers prepared from olefin monomersusing living polymerization catalysts (Domski, G. J.; Rose, J. M.;Coates, G. W.; Bolig, A. D.; Brookhart, M., in Prog. Polym. Sci., 2007;32:30-92). Living polymerization processes employ catalysts having asingle type of active site. Those living polymerization processes thatproduce high yields of block copolymers essentially involve onlyinitiation and propagation steps and essentially lack chain terminatingside reactions. The living polymerization processes are characterized byan initiation rate which is on the order of or exceeds the propagationrate, and essentially the absence of termination or transfer reactions.A block copolymer prepared by living polymerization can have a narrow orextremely narrow distribution of molecular weight and can be essentiallymonodisperse (i.e., the molecular weight distribution is essentiallyone).

Examples of block copolymers that can be made by living polymerizationare olefin block copolymers (e.g., poly(ethylene alpha-olefin) blockcopolymers) and, especially, amphiphilic diblock copolymers. Amphiphilicdiblock copolymers comprise hydrophilic and hydrophobic polymer chains.Amphiphilic diblock copolymers are useful for, among other things,surfactants, dispersants, emulsifiers, stabilizers, and antifoamingagents for aqueous mixtures; surface modifiers for plastics; andcompatibilizers in polymer blends and composites (Lu Y. et al.,Syntheses of diblock copolymers polyolefin-b-poly(ε-caprolactone) andtheir applications as the polymeric compatilizer, Polymer, 2005;46:10585-10591). Lu Y. et al. report a discontinuous polymerizationprocess for making polyolefin-b-poly(ε-caprolactone) diblock copolymers.The discontinuous polymerization process polymerizes a select olefinwith a metallocene catalyst system and a chain transfer agent, andisolates a resulting intermediate polyolefin having a terminal hydroxyl.Then in a different reactor, the discontinuous polymerization processconverts the terminal hydroxyl of the intermediate polyolefin to analuminum alkoxide derivative with diethylaluminum chloride, andsubsequently uses the aluminum alkoxide derivative as an initiator foranionic ring opening polymerization of ε-caprolactone to give thepolyolefin-b-poly(ε-caprolactone) diblock copolymer.

Reporting a significant advancement in preparation of olefin blockcopolymers (OBCs), Arriola D J, et al. mention a catalytic system thatproduces olefin block copolymers with alternating semicrystalline andamorphous segments and a number of desirable material properties(Arriola D J, et al., Catalytic Production of Olefin Block Copolymersvia Chain Shuttling Polymerization, Science, 2006; 312: 714-719). Thecatalyst system can use a chain shuttling agent to transfer polymerchains between two distinct catalysts with different monomerselectivities in a single polymerization reactor. The catalyst systemproduces the OBCs under an economically favorable, continuouspolymerization process.

As a result, chain shuttling agents and olefin block copolymers haverecently been an important area of research. PCT International PatentApplication Publication Numbers WO 2005/073283 A1; WO 2005/090425 A1; WO2005/090426 A1; WO 2005/090427 A2; WO 2006/101595 A1; WO 2007/035485 A1;WO 2007/035492 A1; and WO 2007/035493 A2 mention certain CSAs, catalystsystems, and olefin polymer compositions prepared therewith. Forexample, the WO 2007/035493 A2 mentions multicentered CSAs and a processthat uses the multicentered CSAs to prepare olefin polymer compositionsuniquely characterized by a broad, especially a multimodal molecularweight distribution. The multicentered CSAs of WO 2007/035493 A2 arecompounds or molecules containing more than one chain shuttling moietiesjoined by a polyvalent linking group.

There is a need in the art for new chain shuttling agents,polymerization processes of using same to prepare polyolefins, endfunctional polyolefins, and telechelic polyolefins, and the polyolefins,end functional polyolefins, and telechelic polyolefins prepared thereby,process of making amphiphilic diblock and multiblock copolymers, theamphiphilic diblock and multiblock copolymers prepared thereby, andarticles comprising the polyolefins, end functional polyolefins,telechelic polyolefins, and amphiphilic diblock and multiblockcopolymers.

BRIEF SUMMARY OF THE INVENTION

The present specification presents a new invention concept of amultifunctional chain shuttling agent. The invention multifunctionalchain shuttling agent comprises a single compound or molecule that ischaracterizable as being capable of functioning in such a way that atleast one olefin-containing polymeryl chain can be shuttled between twoor more catalytic sites of an olefin polymerization catalyst having twoor more catalytic sites or between two or more olefin polymerizationcatalysts and independently either: (a) a non-olefin polymerizationreaction can be initiated by the multifunctional chain shuttling agent;(b) a functional group of the multifunctional chain shuttling agent canbe characterized as being protected with a protecting group during thechain shuttling, and then incorporated into the olefin-containingpolymeryl chain; or (c) a non-olefin polymerization reaction can beinitiated by the functional group after it has been incorporated intothe olefin-containing polymeryl chain.

In a preferred first embodiment, the multifunctional chain shuttlingagent comprises a compound having one or more moieties capable of chainshuttling, one or more moieties capable of protecting or polymerizationinitiating, and at least one polyvalent linking group. The chainshuttling moieties are different than the protecting/polymerizationinitiating moieties. Each chain shuttling moiety and polymerizationinitiating moiety independently comprises a metal cation, each metal ofthe metal cations independently being tin or a metal of any one ofGroups 2, 12, and 13 of the Periodic Table of the Elements. Eachpolyvalent linking group independently comprises from 2 to 20 carbonatoms; 0, 1, or 2 carbon-carbon double bonds; and from 1 to 4heteroatoms, each heteroatom independently being either an oxygen atom,sulfur atom, hydrogen-substituted nitrogen atom (i.e., N(H)),hydrocarbyl-substituted nitrogen atom, hydrogen-substituted phosphorousatom (i.e., P(H)), or hydrocarbyl-substituted phosphorous atom. Eachmetal cation of a chain shuttling moiety independently is bonded to adifferent carbon atom of a same polyvalent linking group or to a carbonatom of a different polyvalent linking group and each metal cation of apolymerization initiating moiety independently is bonded to a differentheteroatom of a same polyvalent linking group or to a heteroatom of adifferent polyvalent linking group, the metal cations thereby beingspaced apart from each other by the at least one polyvalent linkinggroup.

In a second embodiment, the present invention provides a process forpreparing the invention multifunctional chain shuttling agent, theprocess comprising steps of: contacting a (hydroxy-, thiol- (i.e., —SH),hydrocarbylamino-, amino- (i.e., —NH₂), hydrocarbylphosphino-, orphosphino- (i.e., —PH₂) and vinyl-containing polyvalent group to analkylperhydrocarbylmetal to respectively prepare an organometallicintermediate that is a hydrocarbylmetal vinyl-alkoxide, hydrocarbylmetalvinyl-sulfide, hydrocarbylmetal vinyl-(hydrocarbyl)amine,hydrocarbylmetal vinyl-amine, hydrocarbylmetalvinyl-(hydrocarbyl)phosphine, or hydrocarbylmetal vinyl-phosphine; andcontacting the organometallic intermediate to a hydrocarbylmetalmonohydride, thereby preparing the multifunctional chain shuttlingagent, each metal independently being a cation of tin or a metal of anyone of Groups 2, 12, and 13 of the Periodic Table of the Elements.

In a third embodiment, the present invention provides a process forpreparing a multifunctional composition, the process comprising a stepof: contacting together ingredients comprising the inventionmultifunctional chain shuttling agent, an original olefin polymerizationcatalyst, and an original cocatalyst, the contacting being performedunder catalyst preparing conditions (described later), thereby preparingthe multifunctional composition, the multifunctional composition beingcapable of functioning as a multifunctional chain shuttling agent and anolefin polymerization catalyst.

In a fourth embodiment, the present invention provides themultifunctional composition prepared by the process of the thirdembodiment.

In a fifth embodiment, the present invention provides a process forpreparing a (polyolefin-polyradical)-containing multifunctional chainshuttling agent, the process comprising a step of: contacting togetherreactants comprising one or more olefin polymerization catalysts and atleast one olefin monomer, the one or more olefin polymerizationcatalysts comprising the multifunctional composition of the fourthembodiment and the contacting step being performed under olefinpolymerizing conditions, thereby preparing a(polyolefin-polyradical)-containing multifunctional chain shuttlingagent, the (polyolefin-polyradical)-containing multifunctional chainshuttling agent being a reaction product of the reactants.

In a sixth embodiment, the present invention provides the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent.

In a seventh embodiment, the present invention provides a process forpreparing a telechelic (i.e., terminally-functionalized) polyolefin, theprocess comprising a step of: terminally functionalizing thepolyolefin-polyradical of the (polyolefin-polyradical)-containingmultifunctional chain shuttling agent, thereby preparing a telechelicpolyolefin.

In an eighth embodiment, the present invention provides the telechelicpolyolefin prepared by the process of the seventh embodiment, thetelechelic polyolefin being characterizable as having spaced-apart firstand second terminal functional groups, the process deriving the firstterminal functional group from a chain shuttling moiety and the secondterminal functional group from a polymerization initiating or protectingmoiety, each such moiety being of the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent, the first and second terminal functional groups beingstructurally different from each other.

In a ninth embodiment, the present invention provides an articlecomprising the telechelic polyolefin of the eighth embodiment.

In a tenth embodiment, the present invention provides a process forpreparing an end functional polyolefin, the process comprising a stepof: terminating the polyolefin-polyradical of the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent, thereby preparing an end functional polyolefin of formula (III):H-polyolefin-CH₂—R^(L)—(X—H)_(w) (III), wherein w is an integer of 1 or2; each R^(L) independently is (C₁-C₁₉)alkylene or (C₂-C₁₉)alkenylene;and each X independently is O, S, N((C₁-C₂₀)hydrocarbyl), orP((C₁-C₂₀)hydrocarbyl).

In an eleventh embodiment, the present invention provides the endfunctional polyolefin prepared by the process of the tenth embodiment.

In a twelfth embodiment, the present invention provides an articlecomprising the end functional polyolefin of the eleventh embodiment.

In a thirteenth embodiment, the present invention provides a process forpreparing a polyolefin/polyester, polyolefin/polyether,polyolefin/polyamide, or polyolefin/polyisocyanate multiblockinterpolymer, the process comprising a step of: contacting togetheringredients comprising the (polyolefin-polyradical)-containingmultifunctional chain shuttling agent and a polyester-, polyether-,polyamide-, or polyisocyanate-forming monomer; the contacting step beingperformed under polyester-, polyether-, polyamide-, orpolyisocyanate-forming conditions, thereby preparing apolyolefin/polyester multiblock interpolymer, polyolefin/polyethermultiblock interpolymer, polyolefin/polyamide multiblock interpolymer,or polyolefin/polyisocyanate multiblock interpolymer.

The multifunctional chain shuttling agents are characterizable as havingat least two mutually compatible, yet different functional activities.One of the functional activities comprises a chain shuttling function.Another of the functional activities comprises aprotecting/polymerization initiating function, which comprises aprotecting group function or, in some embodiments, a polymerizationinitiating function, or in some embodiments both. Depending oncircumstances of the use of the multifunctional chain shuttling agents,the chain shuttling function comprises safekeeping apolyolefin-polyradical chain and transferring it to one or moredifferent olefin polymerization catalysts and ultimately back again forsafekeeping. The polymerization initiating function essentially is forinitiating polyester-, polyether-, polyamide-, or polyisocyanate-formingreactions, especially living polymerization reactions comprisingring-opening polyester-, polyether-, polyamide-, orpolyisocyanate-forming reactions.

An advantage of the multifunctional chain shuttling agents is, forexample, the invention's incorporation of two metal-containing,differently functional moieties into a single compound or molecule.Another advantage is that one of the metal-containing, differentlyfunctional moieties is capable of functioning as a chain shuttling groupand another of the metal-containing, differently functional moieties iscapable of functioning as a polymerization initiating group orprotecting group in a continuous polymerization process.

Still another advantage of the multifunctional CSA is related to thedesign of the compound or molecule, which design separates the twodifferent metal-containing, differently functional moieties by amutually compatible linking group. The design provides a means for themetal-containing functional moiety employed for chain shuttling tosuccessfully carry out chain shuttling functional activity in thepresence of the metal-containing functional group employed forpolymerization initiation or group protection. The design also providesa means for terminally functionalizing the polyolefin-polyradical of the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent or a means for initiating polymerization functional activity inthe presence of the metal-containing functional group employed for chainshuttling. Such mutual compatibility between what until now could havebeen considered potentially conflicting functional moieties andactivities is particularly valuable for making amphiphilic diblock andmultiblock copolymers, especially in a continuous polymerizationprocess.

Still an additional advantage is that the present invention provides newprocesses for preparing polyolefins, telechelic polyolefins, andamphiphilic diblock and amphiphilic multiblock copolymers.

Yet another advantage is that at least some of the polyolefin/polyester,polyolefin/polyether, polyolefin/polyamide, or polyolefin/polyisocyanatemultiblock interpolymers are characterizable as having at least oneunique characteristic such as, for example, polydispersity (as indicatedby polydispersity index) and related unique applications (e.g., batteryseparators). Additional advantages of the present invention are possibleas described later.

The polyolefin/polyester, polyolefin/polyether, polyolefin/polyamide, orpolyolefin/polyisocyanate multiblock interpolymers prepared by a processof the present invention are useful for, among other things,surfactants, dispersants, emulsifiers, stabilizers, and antifoamingagents for aqueous mixtures; surface modifiers for plastics; andcompatibilizers in polymer blends and composites. The polyolefin (whichincludes homopolymers and poly(olefin monomer-olefin comonomer) blockcopolymers as described later), telechelic polyolefin, andpolyolefin/polyester, polyolefin/polyether, polyolefin/polyamide, orpolyolefin/polyisocyanate multiblock interpolymers, are also useful innumerous articles and applications such as, for example, making batteryseparators, elastic films for hygiene applications (e.g., for diapercovers); flexible molded goods for appliances, tools, consumer goods(e.g., toothbrush handles), sporting goods, building and construction,automotive, and medical applications; flexible gaskets and profiles forappliance (e.g., refrigerator door gaskets and profiles), building andconstruction, and automotive applications; adhesives for packaging(e.g., for use in manufacturing corrugated cardboard boxes), hygieneapplications, tapes, and labels; and foams for sporting goods (e.g.,foam mats), packaging, consumer goods, and automotive applications.

Additional embodiments are described in the remainder of thespecification, including the claims.

DETAILED DESCRIPTION OF THE INVENTION

In some embodiments, the polyvalent linking group independentlycomprises from 2 to 12, more preferably from 2 to 10, and still morepreferably from 2 to 8 carbon atoms; and from 1 to 4 heteroatoms, eachheteroatom independently being either an O, S, N(H),hydrocarbyl-substituted nitrogen atom, P(H), or hydrocarbyl-substitutedphosphorous atom.

A preferred embodiment of the multifunctional chain shuttling agent is acompound of formula (I):{((R¹)_(y)M¹[{(—CH₂)_(r))_(t)—R^(L)—[(X—)_(s)}_(q)}_(m)M²(R²)_(z)]_(p)]_(n)  (I)or an exchange product thereof,wherein:

-   -   m is an integer of 1, 2, 3, or 4; r is an integer of 1 or 2; t        is an integer of 1 or 2; each of n, p, q, and s is an integer of        1; and when r is 1, then each R^(L) independently is a        (C₁-C₁₉)alkylene or (C₂-C₁₉)alkenylene; or when (a) r is 1 and t        is 2, or (b) r is 2 and t is 1, or (c) each of m and s is 2 and        r and t are each 1, then each R^(L) independently is a trivalent        radical of a (C₃-C₁₉)alkane or (C₃-C₁₉)alkene; or    -   n is an integer of 1, 2, or 3; s is an integer of 1 or 2; p is        an integer of 1 or 2; each of m, q, r, and t is an integer of 1;        and when s and p are each 1, then each R^(L) independently is a        (C₁-C₁₉)alkylene or (C₂-C₁₉)alkenylene; or when (a) s is 1 and p        is 2, or (b) s is 2 and p is 1, then each R^(L) independently is        a trivalent radical of a (C₃-C₁₉)alkane or (C₃-C₁₉)alkene; or    -   q is an integer of 2 or 3; each of m, n, p, r, s, and t is an        integer of 1; and each R^(L) independently is a (C₁-C₁₉)alkylene        or (C₂-C₁₉)alkenylene; or    -   each of m, n, and q is an integer of 1; each of p, r, s, and t        is an integer of 1 or 2; and R^(L) is a tetravalent radical of a        (C₃-C₁₉)alkane or (C₃-C₁₉)alkene, where one of r and t is 1 and        the other of r and t is 2 and one of p and s is 1 and the other        of p and s is 2;    -   y is an integer of 0, 1, or 2 and is chosen such that the sum of        [y plus the multiplicative product of (n times q times r)] is        equal to the formal oxidation state of M¹, i.e., (the formal        oxidation state of M¹)=y+(n·q·r);    -   z is an integer of 0, 1, 2, or 3 and is chosen such that the sum        of [z plus the multiplicative product of (m times q times s)] is        equal to the formal oxidation state of M¹, i.e., (the formal        oxidation state of M¹)=z+(m·q·s);    -   Each X independently is O, S, N(H), N((C₁-C₂₀)hydrocarbyl),        P(H), P((C₁-C₂₀)hydrocarbyl);    -   Each M¹ is a metal of Group 2, 12, or 13 of the Periodic Table        of the Elements, the Group 13 metal being in a formal oxidation        state of +3 and the Group 2 or 12 metal being in a formal        oxidation state of +2;    -   Each M² is tin or a metal of Group 12 or 13 of the Periodic        Table of the Elements, the Group 12 metal being in a formal        oxidation state of +2, the Group 13 metal being in a formal        oxidation state of +3, and the tin being in a formal oxidation        state of +2 or +4;    -   Each R¹ independently is a (C₁-C₂₀)hydrocarbyl; or, when y is 2,        one R¹ is (C₁-C₂₀)hydrocarbyl and one R¹ is R³N(H)—, (R³)₂N—,        R³P(H)—, (R³)₂P—, R³S—, or R³O—, or two R¹ are taken together to        form a (C₂-C₂₀)hydrocarbylene; and    -   Each R² independently is a hydrogen, (C₁-C₂₀)hydrocarbyl or        -D-(C₁-C₂₀)hydrocarbyl; or, when z is 2 or 3, two R² are taken        together to form a (C₂-C₂₀)hydrocarbylene;    -   Each D, as shown in the -D-(C₁-C₂₀)hydrocarbyl, independently is        —C(═O)—, —C(═O)—O—, —O—C(═O)—, —C(═O)—N((C₁-C₆)hydrocarbyl)-,        —N((C₁-C₆)hydrocarbyl)-C(═O)—, —S(═O)—, —S(═O)₂—, or        —Si((C₁-C₂₀)hydrocarbyl)₂-;    -   Each R³ independently is a (C₁-C₂₀)hydrocarbyl or        ((C₁-C₂₀)hydrocarbyl)₃Si—;    -   Each of the aforementioned (C₁-C₁₉)alkylene, (C₂-C₁₉)alkenylene,        (C₃-C₁₉)alkane, (C₃-C₁₉)alkene, (C₁-C₂₀)hydrocarbyl, and        (C₂-C₂₀)hydrocarbylene are the same or different and        independently is unsubstituted or substituted with one or more        substituents R^(s); and    -   Each R^(s) independently is halo, polyfluoro, perfluoro,        unsubstituted (C₁-C₁₈)alkyl, or unsubstituted (C₁-C₉)heteroaryl.

A more preferred embodiment of the multifunctional chain shuttling agentof formula (I) that is a compound of formula (IA):{(R¹)_(y)M¹-[CH₂—R^(L)—[X—}_(m)M²(R²)_(z)]_(p)]_(n)  (IA)or an exchange product thereof,wherein:

-   -   m is an integer of 1, 2, 3, or 4, each of n and p is an integer        of 1, and each R^(L) independently is a (C₁-C₁₉)alkylene or        (C₂-C₁₉)alkenylene; or    -   n is an integer of 1, 2, or 3, each of m and p is an integer of        1, and each R^(L) independently is a (C₁-C₁₉)alkylene or        (C₂-C₁₉)alkenylene; or    -   p is an integer of 2, each of m and n is an integer of 1, and        R^(L) is a trivalent radical of a (C₃-C₁₉)alkane or        (C₃-C₁₉)alkene;    -   y is an integer of 0, 1, or 2 and is chosen such that a sum of        y+n is equal to the formal oxidation state of M¹;    -   z is an integer of 0, 1, 2, or 3 and is chosen such that a sum        of z+m is equal to the formal oxidation state of M²; and    -   X, M¹, M², R¹, and R² are as defined previously for formula (I);    -   or    -   Each of m, n, and p is 1, (R¹)_(y)M¹ is absent and M², R², and        z, are as defined previously for formula (I).

In the diradical group D, and the like, the —C(═O)— means carbonyl,—C(═O)—O— means a carboxyl diradical (C and O radicals, C radical beingbonded to M²), —O—C(═O)— means a carboxyl diradical (O and C radicals, Oradical being bonded to M²), —C(═O)—N((C₁-C₆)hydrocarbyl)- means anN—(C₁-C₆)hydrocarbyl)-substituted carboxamido diradical (C and Nradicals, C radical being bonded to M²), —N((C₁-C₆)hydrocarbyl)-C(═O)—means an N—(C₁-C₆)hydrocarbyl)-substituted carboxamido diradical (N andC radicals, N radical being bonded to M²), —S(═O)— means sulfinyl (alsocalled thionyl), —S(═O)₂— means sulfonyl, and —Si((C₁-C₂₀)hydrocarbyl)₂-means a di((C₁-C₆)hydrocarbyl)-substituted silyl diradical.

In some embodiments where each of m, n, and p is 1, (R¹)_(y)M¹ isabsent, M² is taken together with the CH₂ in formula (IA) to form amultifunctional chain shuttling agent of formula (II):

or an exchange product thereof, wherein g is an integer of 0, 1, or 2and is chosen such that a sum of (g+2q) is equal to the formal oxidationstate of M²; q is defined as for the compound of formula (I), and R^(L),X, M², and R² are as defined for the compound of formula (IA). Insolution, the multifunctional chain shuttling agent of formula (II) maybe characterizable as forming an acyclic oligomeric structure.

In the multifunctional chain shuttling agent of formula (I), each group(R¹)yM¹-CH₂ comprises an example of the chain shuttling, metalcation-containing moiety, the CH₂ being derived from the polyvalentlinking group CH₂—R^(L). Each group X-M²(R₂)_(z) comprises an example ofthe protecting/polymerization initiating, metal cation-containingmoiety. The protecting group moiety comprises a protecting group for—OH, —SH, —NH₂, —N(H)(C₁-C₂₀)hydrocarbyl, —PH₂, or—P(H)(C₁-C₂₀)hydrocarbyl. Preferably, the protecting group comprises theM² (e.g., M²(R²)_(z) or an exchange product thereof). The R^(L) portionof the polyvalent linking group, CH₂—R^(L), compatibly links the one ormore chain shuttling moieties to the one or moreprotecting/polymerization initiating moieties.

In another embodiment, the present invention provides a process forpreparing the compound of formula (I):{((R¹)_(y)M¹[{(—CH₂)_(r))_(t)—R^(L)—[(X—)_(s)}_(q)}_(m)M²(R²)_(z)]_(p)]_(n)  (I)or an exchange product thereof, the process comprising steps of:

-   -   (a) contacting together an alkylperhydrocarbylmetal of formula        (1):        M²(C₁-C₂₀)alkyl)(R²)_(z)  (1),        wherein M², R² and z are as defined previously in the first        embodiment,        and a (hydroxy-, thiol-, amino-, hydrocarbylamino-, phosphino-,        or hydrocarbylphosphino-) and vinyl-containing polyvalent group        of formula (2):        [H₂C═C(R⁴)]_(r)—R^(L1)—[XH]_(p)  (2),        wherein R⁴ is hydrogen or a (C₁-C₅)alkyl and R^(L1) is absent or        a polyvalent radical of a (C₁-C₁₈)hydrocarbon, the        (C₁-C₁₈)hydrocarbon being saturated or mono- or di-unsaturated        and R⁴ and R^(L1) being selected so that the number t C(R⁴)        groups and R^(L1) have a total number of carbon atoms of from 1        to 19 carbon atoms; and X, p and r are as defined previously in        the first embodiment, to give a hydrocarbylmetal        vinyl-alkoxide/sulfide/amide/phosphide of formula (3):        [H₂C═C(R⁴)]_(r)—R^(L1)—[X-M²(R²)_(z)]_(p)  (3);        and    -   (b) contacting the hydrocarbylmetal        vinyl-alkoxide/sulfide/amide/phosphide of formula (3) to n mole        equivalents of a hydrocarbylmetal monohydride of formula (4):        HM¹(R¹)_(y)  (4)        wherein y, M¹, and R¹ are as defined previously in the first        embodiment, to give the multifunctional chain shuttling agent of        formula (I):        {((R¹)_(y)M¹[{(—CH₂)_(r))_(t)—R^(L)—[(X—)_(s)}_(q)}_(m)M²(R²)_(z)]_(p)]_(n)  (I),        or an exchange product thereof,        wherein R^(L), X, R¹, R², M¹, M², m, n, p, q, r, s, t, y, and z        are as defined previously.

In some embodiments, the (polyolefin-polyradical)-containingmultifunctional chain shuttling agent is characterizable as beingcapable of functioning as a chain shuttling agent, a polymerizationinitiating agent, a protecting agent, or any combination thereof. Insome embodiments, the (polyolefin-polyradical)-containingmultifunctional chain shuttling agent is characterizable as beingcapable of functioning as an intermediate in a process for preparing theinvention telechelic polyolefin, polyolefin, polyolefin/polyether,polyolefin/polyamide, or polyolefin/polyisocyanate multiblockinterpolymer, or polyolefin/polyester multiblock interpolymer.

The term “polyolefin-polyradical” means a polymeric group comprisingresiduals of at least one olefin monomer and two or more radicals. Thepolyolefin-polyradical is formally obtained by removing a hydrogen atomfrom each of at least two carbon atoms. In some embodiments, thepolyolefin-polyradical of the (polyolefin-polyradical)-containingmultifunctional chain shuttling agent comprises from 2 to 5 radicals,more preferably 2 or 3 radicals, and still more preferably 2 radicals.

In some embodiments, the reactants in the process of the fifthembodiment further comprise an associate olefin polymerization catalystand an olefin comonomer, the associate olefin polymerization catalystbeing characterizable as being chemically different from, and havingdifferent selectivities for the olefin monomer than, the original olefinpolymerization catalyst; the prepared(polyolefin-polyradical)-containing multifunctional chain shuttlingagent being a poly(olefin monomer-olefincomonomer)-polyradical-containing multifunctional chain shuttling agent.In some embodiments, the associate olefin polymerization catalyst isactivated with the original cocatalyst. In some embodiments, thereactants further comprise an associate cocatalyst, the associatecocatalyst being for activating the associate olefin polymerizationcatalyst. The terms “original olefin polymerization catalyst” and“associate olefin polymerization catalyst” are used for convenience todistinguish between two (or more) different catalysts when describingcertain embodiments of the invention process. Likewise, the terms“original cocatalyst” and “associate cocatalyst” are used forconvenience to distinguish between two (or more) different cocatalystswhen describing certain embodiments of the invention process.

Where the reactants in the process of the fifth embodiment furthercomprise the associate olefin polymerization catalyst and the olefincomonomer as described previously, the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent produced thereby and of the sixth embodiment is a poly(olefinmonomer-olefin comonomer)-containing multifunctional chain shuttlingagent.

In some embodiments, preferably the (polyolefin-polyradical)-containingmultifunctional chain shuttling agent is the poly(olefin monomer-olefincomonomer)-polyradical-containing multifunctional chain shuttling agentand the polyolefin is the poly(olefin monomer-olefin comonomer). Thusare provided preferred aspects of the seventh through thirteenthembodiments that respectively are: (7^(th)): a process for preparing atelechelic poly(olefin monomer-olefin comonomer); (8^(th)): thetelechelic poly(olefin monomer-olefin comonomer), the telechelicpoly(olefin monomer-olefin comonomer) being characterizable as having anon-statistical distribution of terminal functional groups; (9^(th)): anarticle comprising the telechelic poly(olefin monomer-olefin comonomer);(10^(th)): a process for preparing an end functional poly(olefinmonomer-olefin comonomer); (11^(th)): the end functional poly(olefinmonomer-olefin comonomer); (12^(th)): an article comprising the endfunctional poly(olefin monomer-olefin comonomer); and (13^(th)): aprocess for preparing a poly(olefin monomer-olefin comonomer)/polyester,poly(olefin monomer-olefin comonomer)/polyether, poly(olefinmonomer-olefin comonomer)/polyamide, or poly(olefin monomer-olefincomonomer)/polyisocyanate multiblock interpolymer.

In any embodiment, preferably each polyolefin-polyradical being apoly(olefin monomer-olefin comonomer)-polyradical and each polyolefinbeing a poly(olefin monomer-olefin comonomer) multiblock copolymer.

Preferably, the (polyolefin-polyradical)-containing multifunctionalchain shuttling agent comprises a composition of formula (IV):{(R¹)_(y)M¹-[(polyolefin-polyradical)-CH₂—R^(L)—[X}_(m) M²(R²)_(z)]_(p)]_(n)  (IV)or an exchange product thereof, and the poly(olefin monomer-olefinpolyradical)-containing multifunctional chain shuttling agent comprisesa composition of formula (IVa):{(R¹)_(y)M¹-[poly(olefin monomer-olefinpolyradical))-CH₂—R^(L)—[X}_(m)M²(R²)_(z)]_(p)]_(n)  (IVa)or an exchange product thereof, where in formulas (IV) and (IVa): R¹,R², y, M¹, R^(L), X, m, M², z, p, and n are as defined in the firstembodiment, or a reaction product of two or more of the reactants in theprocess of the fifth embodiment. An example of the reaction product isthe composition of formula (IV) or (IVa) where R¹, R², or R¹ and R²independently are residuals of a reaction product of the olefin monomer.Another example is for the composition of formula (IVa), one or both ofR¹ and R² independently are residuals of a reaction product of theolefin comonomer.

As mentioned previously for step (a) of the process of the fifthembodiment, the process further employs, and the multifunctionalcomposition of the fourth embodiment further comprises, the associateolefin polymerization catalyst. In such embodiments, the original andassociate olefin polymerization catalysts are independently employed insame or different catalytic amounts; the original and associatecocatalysts are independently employed in same or different cocatalyticamounts; and the invention multifunctional chain shuttling agent beingcharacterizable, without limitation, as functioning in step (a) in sucha way that polymer chains are transferred back-and-forth between theoriginal and associate olefin polymerization catalysts.

The invention polymers are sometimes collectively referred to herein asthe instant block interpolymers. The term “poly(ethylene alpha-olefin)block copolymer” is used interchangeably herein with the terms “olefinblock copolymer,” “OBC,” “ethylene/α-olefin block interpolymer,” and“ethylene/α-olefin block copolymer”. The terms “alpha-olefin” and“α-olefin” are used interchangeably herein.

For purposes of United States patent practice and other patent practicesallowing incorporation of subject matter by reference, the entirecontents—unless otherwise indicated—of each U.S. patent, U.S. patentapplication, U.S. patent application publication, PCT internationalpatent application and WO publication equivalent thereof, referenced inthe instant Summary or Detailed Description of the Invention are herebyincorporated by reference. In an event where there is a conflict betweenwhat is written in the present specification and what is written in apatent, patent application, or patent application publication, or aportion thereof that is incorporated by reference, what is written inthe present specification controls.

In the present application, any lower limit of a range of numbers, orany preferred lower limit of the range, may be combined with any upperlimit of the range, or any preferred upper limit of the range, to definea preferred aspect or embodiment of the range. Each range of numbersincludes all numbers, both rational and irrational numbers, subsumedwithin that range (e.g., the range from about 1 to about 5 includes, forexample, 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

In an event where there is a conflict between a compound name and itsstructure, the structure controls.

In an event where there is a conflict between a unit value that isrecited without parentheses, e.g., 2 inches, and a corresponding unitvalue that is parenthetically recited, e.g., (5 centimeters), the unitvalue recited without parentheses controls.

As used herein, “a,” “an,” “the,” “at least one,” and “one or more” areused interchangeably. In any aspect or embodiment of the instantinvention described herein, the term “about” in a phrase referring to anumerical value may be deleted from the phrase to give another aspect orembodiment of the instant invention. In the former aspects orembodiments employing the term “about,” meaning of “about” can beconstrued from context of its use. Preferably “about” means from 90percent to 100 percent of the numerical value, from 100 percent to 110percent of the numerical value, or from 90 percent to 110 percent of thenumerical value. In any aspect or embodiment of the instant inventiondescribed herein, the open-ended terms “comprising,” “comprises,” andthe like (which are synonymous with “including,” “having,” and“characterized by”) may be replaced by the respective partially closedphrases “consisting essentially of,” consists essentially of,” and thelike or the respective closed phrases “consisting of,” “consists of,”and the like to give another aspect or embodiment of the instantinvention. In the present application, when referring to a precedinglist of elements (e.g., ingredients), the phrases “mixture thereof,”“combination thereof,” and the like mean any two or more, including all,of the listed elements. The term “or” used in a listing of members,unless stated otherwise, refers to the listed members individually aswell as in any combination, and supports additional embodiments recitingany one of the individual members (e.g., in an embodiment reciting thephrase “10 percent or more,” the “or” supports another embodimentreciting “10 percent” and still another embodiment reciting “more than10 percent.”). The term “plurality” means two or more, wherein eachplurality is independently selected unless indicated otherwise.

Unless otherwise noted, the phrase “Periodic Table of the Elements”refers to the official periodic table, version dated Jun. 22, 2007,published by the International Union of Pure and Applied Chemistry(IUPAC). Also any references to a Group or Groups shall be to the Groupor Groups reflected in this Periodic Table of the Elements.

Unless otherwise noted, the general term “hydrocarbyl” preferably is a(C₁-C₂₀)hydrocarbyl. As used herein, the term “(C₁-C₂₀)hydrocarbyl”means a hydrocarbon radical of from 1 to 20 carbon atoms and the term“(C₂-C₂₀)hydrocarbylene” means a hydrocarbon diradical of from 2 to 20carbon atoms, wherein each hydrocarbon radical and diradicalindependently is aromatic or non-aromatic, saturated or unsaturated,straight chain or branched chain, cyclic (including mono- andpoly-cyclic, fused and non-fused polycyclic) or acyclic, or acombination of two or more thereof; and each hydrocarbon radical anddiradical is the same as or different from another hydrocarbon radicaland diradical, respectively, and independently substituted by one ormore R^(s) or, preferably, unsubstituted.

Preferably, a (C₁-C₂₀)hydrocarbyl independently is an unsubstituted orsubstituted (C₁-C₂₀)alkyl, (C₃-C₂₀)cycloalkyl,(C₃-C₁₀)cycloalkyl-(C₁-C₁₀)alkylene, (C₆-C₂₀)aryl, or(C₆-C₁₀)aryl-(C₁-C₁₀)alkylene. More preferably, each of theaforementioned groups independently has a maximum of 18 carbon atoms(e.g., (C₁-C₁₈)alkyl, (C₃-C₁₈)cycloalkyl,(C₃-C₉)cycloalkyl-(C₁-C₉)alkylene, (C₆-C₁₈)aryl, or(C₆-C₁₀)aryl-(C₁-C₈)alkylene), still more preferably 12 carbon atoms(e.g., (C₁-C₁₂)alkyl, (C₃-C₁₂)cyclo alkyl,(C₃-C₈)cycloalkyl-(C₁-C₄)alkylene, (C₆-C₁₂)aryl, or(C₆)aryl-(C₁-C₆)alkylene).

The term “(C₁-C₂₀)alkyl” means a saturated straight or branchedhydrocarbon radical of from 1 to 20 carbon atoms that is unsubstitutedor substituted by one or more R^(s). Preferably, (C₁-C₂₀)alkyl has amaximum of 18 carbon atoms, more preferably 12 carbon atoms, still morepreferably 8 carbon atoms. Examples of unsubstituted (C₁-C₂₀)alkyl areunsubstituted (C₁-C₁₈)alkyl; unsubstituted (C₁-C₁₀)alkyl; unsubstituted(C₁-C₅)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl;2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl;and 1-decyl. Examples of substituted (C₁-C₂₀)alkyl are substituted(C₁-C₁₈)alkyl, substituted (C₁-C₁₀)alkyl, trifluoromethyl, and(C₂₅)alkyl. Preferably, each (C₁-C₅)alkyl independently is methyl,ethyl, 1-propyl, or 2-methylethyl.

The term “(C₆-C₂₀)aryl” means an unsubstituted or substituted (by one ormore R^(s)) mono-, bi- or tricyclic aromatic hydrocarbon radical of from6 to 20 total carbon atoms, of which at least from 6 to 14 are ringcarbon atoms, and the mono-, bi- or tricyclic radical respectivelycomprises 1, 2 or 3 rings, wherein the 2 or 3 rings independently arefused or non-fused and the 1 ring is aromatic and at least one of the 2or 3 rings is aromatic. Preferably, (C₆-C₂₀)aryl has a maximum of 18carbon atoms, more preferably 10 carbon atoms, still more preferably 6carbon atoms. Examples of unsubstituted (C₆-C₂₀)aryl are unsubstituted(C₆-C₁₈)aryl; 2-(C₁-C₅)alkyl-phenyl; 2,4-bis(C₁-C₅)alkyl-phenyl;2,4,6-tris(C₁-C₅)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl;indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl;tetrahydronaphthyl; anthracenyl; and phenanthrenyl. Examples ofsubstituted (C₆-C₂₀)aryl are substituted (C₆-C₁₈)aryl;2,4-bis[(C₆)alkyl]-phenyl; polyfluorophenyl; pentafluorophenyl; andfluoren-9-one-1-yl.

The term “(C₃-C₂₀)cycloalkyl” means a saturated cyclic hydrocarbonradical of from 3 to 20 carbon atoms that is unsubstituted orsubstituted by one or more R^(s). Preferably, (C₃-C₂₀)cycloalkyl has amaximum of 18 carbon atoms, more preferably 12 carbon atoms, still morepreferably 6 carbon atoms. Examples of unsubstituted (C₃-C₂₀)cycloalkylare unsubstituted (C₃-C₁₂)cycloalkyl, unsubstituted (C₃-C₁₀)cycloalkyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted(C₃-C₂₀)cycloalkyl are substituted (C₃-C₁₂)cycloalkyl, substituted(C₃-C₁₀)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

Thus, (C₂-C₂₀)hydrocarbylene means an unsubstituted or substituteddiradical analog of (C₆-C₂₀)aryl, (C₃-C₂₀)cycloalkyl, or (C₂-C₂₀)alkyl,i.e., (C₆-C₂₀)arylene, (C₃-C₂₀)cycloalkylene, and (C₂-C₂₀)alkylene,respectively. More preferably, each of the aforementioned groupsindependently has a maximum of 20 carbon atoms (e.g., (C₆-C₁₈)arylene,(C₃-C₂₀)cycloalkylene, and (C₂-C₂₀)alkylene), still more preferably 12carbon atoms (e.g., (C₆-C₁₂)arylene, (C₃-C₁₂)cycloalkylene, and(C₂-C₁₂)alkylene). In some embodiments, the diradicals are on adjacentcarbon atoms (i.e., 1,2-diradicals), or spaced apart by one, two, ormore intervening carbon atoms (e.g., respective 1,3-diradicals,1,4-diradicals, etc.). Preferred is a 1,2-, 1,3-, 1,4-, oralpha,omega-diradical, more preferably a 1,2-diradical.

The term “(C₁-C₁₉)alkylene” means a saturated straight or branched chaindiradical of from 1 to 19 carbon atoms that is unsubstituted orsubstituted by one or more R^(s). Examples of unsubstituted(C₁-C₁₉)alkylene are unsubstituted (C₁-C₁₂)alkylene, includingunsubstituted 1,2-(C₁-C₁₂)alkylene and unsubstituted (C₁-C₇)alkylene.Examples of unsubstituted (C₁-C₇)alkylene are —CH₂—, —CH₂CH₂—, —(CH₂)₃—,

—(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, and —(CH₂)₅C(H)(CH₃)—. Examples ofsubstituted (C₁-C₁₉)alkylene are substituted (C₁-C₁₀)alkylene,substituted (C₁-C₇)alkylene, —CF₂—, and —(CH₂)₁₄C(CH₃)₂(CH₂)₅— (i.e., a6,6-dimethyl substituted normal-1,20-eicosylene).

The term “(C₂-C₁₉)alkenylene” means a mono- or di-unsaturated, saturatedstraight or branched chain diradical of from 2 to 19 carbon atoms thatis unsubstituted or substituted by one or more R^(s). Preferably, the(C₂-C₁₉)alkenylene is mono-unsaturated, that is, contains 1carbon-carbon double bond.

The terms “(C₃-C₁₉)alkane” and “(C₃-C₆)alkane” means a hydrocarbonmolecule comprising from 3 to 19 or from 3 to 6 carbon atoms,respectively, the molecule being unsubstituted or substituted,saturated, acyclic or cyclic, straight or branched.

The term “(C₃-C₁₉)alkene” means a mono- or di-unsaturated hydrocarbonmolecule comprising from 3 to 19 carbon atoms, the molecule beingunsubstituted or substituted, acyclic or cyclic, straight or branched.Preferably, the (C₃-C₁₉)alkene is mono-unsaturated, that is, contains 1carbon-carbon double bond.

The term “(C₁-C₉)heteroaryl” means an unsubstituted or substituted (byone or more R^(s)) mono- or bicyclic heteroaromatic cyclic radical offrom 1 to 9 ring carbon atoms and from 1 to 4 ring heteroatoms, theheteroatoms independently being oxygen, nitrogen, phosphorous, orsulfur. The monocyclic and bicyclic heteroaromatic radicals comprise 1or 2 rings, respectively, wherein the 2 rings of the bicyclicheteroaromatic radical independently are fused or non-fused to eachother and at least one of the 2 rings is aromatic. Preferably, the(C₁-C₉)heteroaryl is a 5- or 6-membered monocycle or a 9- or 10-memberedbicycle. Examples of unsubstituted (C₁-C₉)heteroaryl are unsubstituted(C₁-C₄)heteroaryl, pyrrol-1-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl;isoxazol-2-yl; isothiazol-5-yl; imidazol-1-yl; oxazol-4-yl;thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl;1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; pyridine-2-yl;pyrimidin-2-yl; pyrazin-2-yl; indol-1-yl; benzimidazole-1-yl;quinolin-2-yl; and isoquinolin-1-yl.

The term “halo” means fluoro (—F), chloro (—Cl), bromo (—Br), or iodo(—I) radical. Preferably, halo is fluoro or chloro, more preferablyfluoro. The term “halide” means fluoride (F⁻), chloride (Cl⁻), bromide(Br⁻), or iodide (I⁻) anion.

Preferably, there are no O—O, S—S, or O—S bonds, other than O—S bonds inan S(O) or S(O)₂ diradical functional group, in the multifunctional CSAof formula (I).

The term “saturated” means lacking carbon-carbon double bonds,carbon-carbon triple bonds, and (in heteroatom-containing groups)carbon-nitrogen, carbon-phosphorous, and carbon-silicon double bonds.Where a saturated chemical group is substituted by one or moresubstituents R^(s), one or more double and/or triple bonds optionallymay or may not be present in substituents R^(s). The term “unsaturated”means containing one or more carbon-carbon double bonds, carbon-carbontriple bonds, and (in heteroatom-containing groups) carbon-nitrogen,carbon-phosphorous, and carbon-silicon double bonds, not including anysuch double bonds that may be present in substituents R^(s), if any, orin (hetero)aromatic rings, if any.

The term, “chain shuttling agent” refers to a compound such as themultifunctional CSA of formula (I) or mixture of such compounds that iscapable of causing polymeryl (i.e., polymer chain) exchange between atleast two active catalyst sites of the original and associate olefinpolymerization catalysts under the olefin polymerization conditions.That is, transfer of a polymer fragment occurs both to and from one ormore of active sites of the olefin polymerization catalysts.

In contrast to a chain shuttling agent, a “chain transfer agent” causestermination of polymer chain growth and amounts to a one-time transferof polymer from a catalyst to the transfer agent. In some polymerizationprocess embodiments such as those useful for preparing polyolefinhomopolymers and random polyolefin copolymers, the multifunctional CSAis characterizable as functioning as a chain transfer agent. That is,the multifunctional CSA is characterizable as functioning in such a waythat there is a one-time transfer of a polyolefin homopolymer or randompolyolefin copolymer product formed in such polymerization process fromthe olefin polymerization catalyst to the multifunctional CSA. In suchembodiments, it is not necessary for the multifunctional CSA toreversibly chain shuttle, as such embodiments typically employ only oneolefin polymerization catalyst, which may have or use only one activecatalyst site.

In some embodiments, the invention multifunctional chain shuttling agentis characterizable as having a chain shuttling activity ratioR_(A-B)/R_(B-A). In general, for any two catalysts (A) and (B), thechain shuttling activity ratio R_(A-B)/R_(B-A) is calculated by dividinga rate of chain transfer from an active site of a catalyst (A) to anactive site of a catalyst (B) (R_(A-B)) by a rate of chain transfer fromthe active site of the catalyst (B) to the active site of the catalyst(A) (R_(B-A)). For the invention multifunctional chain shuttling agent,preferably the chain shuttling activity ratio R_(A-B)/R_(B-A) is from0.01 to 100, more preferably from 0.1 to 10, still more preferably from0.5 to 2.0, and even more preferably from 0.8 to 1.2. Preferably, anintermediate formed between the invention multifunctional chainshuttling agent and the polymeryl chain is sufficiently stable thatchain termination is relatively rare. The(polyolefin-polyradical)-containing multifunctional chain shuttlingagent is an example of said intermediates.

By selecting different combinations of olefin polymerization catalystshaving differing comonomer incorporation rates (as described herein) aswell as differing reactivities, and by combining the inventionmultifunctional chain shuttling agent with one or more additional chainshuttling agents, the additional chain shuttling agents comprising oneor more additional multifunctional chain shuttling agents of formula(I), or one or more non-invention chain shuttling agents, or acombination thereof, different poly(olefin monomer-olefin comonomer)multiblock copolymer products can be prepared. Such different productscan have segments of different densities or comonomer concentrations,different block lengths, different numbers of such segments or blocks,or a combination thereof. For example, if the chain shuttling activityof the invention multifunctional chain shuttling agent is low relativeto a polymer chain propagation rate of one or more of the catalysts,longer block length multiblock copolymers and polymer blends may beobtained as products. Contrariwise, if chain shuttling is very fastrelative to polymer chain propagation, a copolymer product having a morerandom chain structure and shorter block lengths is obtained. Ingenerally, an extremely fast chain shuttling agent may produce amultiblock copolymer having substantially random copolymer properties.By proper selection of both catalyst(s) and the inventionmultifunctional chain shuttling agent, relatively pure block copolymers,copolymers containing relatively large polymer segments or blocks,and/or blends of the foregoing with various ethylene homopolymers and/orcopolymers can be obtained as products.

Where the invention comprises or employs at least one additional chainshuttling agent as described previously, preferably the inventioncomprises or employs a total of 3 or fewer, and more preferably a totalof 2 chain shuttling agents, at least one of the total number of chainshuttling agents being the multifunctional chain shuttling agent offormula (I). Preferably the invention does not comprise or employ anynon-invention chain shuttling agent. In some embodiments, however, itmay be desirable to employ one or more non-invention chain shuttlingagents. The non-invention chain shuttling agents that are suitable forcombining with the invention multifunctional chain shuttling agentinclude Group 1, 2, 12 or 13 metal compounds or complexes containing atleast one (C₁-C₂₀)hydrocarbyl group, preferably (C₁-C₁₂)hydrocarbylsubstituted aluminum, gallium or zinc compounds, and reaction productsthereof with a proton source. Preferred (C₁-C₂₀)hydrocarbyl groups arealkyl groups, preferably linear or branched, (C₁-C₈)alkyl groups. Mostpreferred shuttling agents for use in the present invention are trialkylaluminum and dialkyl zinc compounds, especially triethylaluminum,tri(i-propyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum,tri(n-octyl)aluminum, triethylgallium, or diethylzinc. Additionalsuitable shuttling agents include the reaction product or mixture formedby combining the foregoing organometal compound, preferably atri((C₁-C₈)alkyl)aluminum or di((C₁-C₈)alkyl)zinc compound, especiallytriethylaluminum, tri(i-propyl)aluminum, tri(i-butyl)aluminum,tri(n-hexyl)aluminum, tri(n-octyl)aluminum, or diethylzinc, with lessthan a stoichiometric quantity (relative to the number of hydrocarbylgroups) of a primary or secondary amine, primary or secondary phosphine,thiol, or hydroxyl compound, especially bis(trimethylsilyl)amine,t-butyl(dimethyl)silanol, 2-hydroxymethylpyridine, di(n-pentyl)amine,2,6-di(t-butyl)phenol, ethyl(1-naphthyl)amine,bis(2,3,6,7-dibenzo-1-azacycloheptaneamine), diphenylphosphine,2,6-di(t-butyl)thiophenol, or 2,6-diphenylphenol. Desirably, sufficientamine, phosphine, thiol, or hydroxyl reagent is used such that at leastone hydrocarbyl group remains per metal atom. The primary reactionproducts of the foregoing combinations most desired for use in thepresent invention as shuttling agents are n-octylaluminumdi(bis(trimethylsilyl)amide), i-propylaluminumbis(dimethyl(t-butyl)siloxide), and n-octylaluminumdi(pyridinyl-2-methoxide), i-butylaluminumbis(dimethyl(t-butyl)siloxane), i-butylaluminumdi(bis(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide),i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide), n-octylaluminumdi(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide),ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide). Other suitable non-invention chain shuttlingagents are described in WO 2005/073283 A1; WO 2005/090425 A1; WO2005/090426 A1; WO 2005/090427 A2; WO 2006/101595 A1; WO 2007/035485 A1;WO 2007/035492 A1; and WO 2007/035493 A2.

The term “exchange product thereof” means a molecule or oligomericsubstance derived by intramolecular redistribution of two or moreligands to M¹ or M², or by at least one ligand to M¹ and at least oneligand to M², or by intermolecular redistribution between at least oneof said ligands of one molecule of formula (I) and at least one of saidligands of another molecule of formula (I); or a combination of theintramolecular and intermolecular redistributions. The ligands to M¹refer to R¹ and the “CH₂” in formula (I). The ligands to M² refer to R²and the “X” in formula (I). The term “exchange product” may also bereferred to herein as a “redistribution product.” The inventioncontemplates exchange products of any invention multifunctional chainshuttling agent, including the multifunctional chain shuttling agent ofany one of formulas (I) and (IV).

Examples of exchange products of the compound of formula (I) arecompounds of formulas (IB) and (IC),

the compounds of formulas (IB) and (IC) having divalent R^(L) groups;and compounds of formulas (ID) to (IK):

wherein the compounds of formulas (ID), (IE), and (IG) to (IK) havetrivalent R^(L) groups and the compounds of formulas (IF1) to (IF4) havetetravalent R^(L) groups. (Formula designation “(II),” i.e., pronounced“one i,” has been purposely omitted from the immediately precedingstructure designations in order to avoid confusion with theaforementioned formula (II), i.e., where the “(II)” is a Roman numeraltwo.)

In some embodiments of the multifunctional CSA of formula (I), m is aninteger of 1, 2, 3, or 4; r is an integer of 1 or 2; t is an integer of1 or 2; each of n, p, q, and s is an integer of 1, that is amultifunctional CSA of formula (Im):{((R¹)_(y)M¹(—CH₂)_(r))_(t)—R^(L)—X—}_(m)M²(R²)_(z)  (Im)or an exchange product thereof, and when r is 1, then each R^(L)independently is a (C₁-C₁₉)alkylene or (C₂-C₁₉)alkenylene; or when (a) ris 1 and t is 2, or (b) r is 2 and t is 1, or (c) each of m and s is 2and r and t are each 1, then each R^(L) independently is a trivalentradical of a (C₃-C₁₉)alkane or (C₃-C₁₉)alkene; and y, z, X, M¹, M², R¹,and R² are as defined previously for formula (I).

In some embodiments of the multifunctional CSA of formula (I), n is aninteger of 1, 2, or 3; is an integer of 1 or 2; p is an integer of 1 or2; each of m, q, r, and t is an integer of 1, that is a multifunctionalCSA of formula (In):(R¹)_(y)M¹[—CH₂—R^(L)—[(X—)_(s)M²(R²)_(z)]_(p)]_(n)  (In)or an exchange product thereof, and when s and p are each 1, then eachR^(L) independently is a (C₁-C₁₉)alkylene or (C₂-C₁₉)alkenylene; or when(a) s is 1 and p is 2, or (b) s is 2 and p is 1, then each R^(L)independently is a trivalent radical of a (C₃-C₁₉)alkane or(C₃-C₁₉)alkene; and y, z, X, M¹, M², R¹, and R² are as definedpreviously for formula (I).

In some embodiments of the multifunctional CSA of formula (I), q is aninteger of 2 or 3; each of m, n, p, r, s, and t is an integer of 1, thatis a multifunctional CSA of formula (Iq):((R¹)_(y)M¹{—CH₂—R^(L)—X—}_(q)M²(R²)_(z)  (Iq)or an exchange product thereof, and each R^(L) independently is a(C₁-C₁₉)alkylene or (C₂-C₁₉)alkenylene; and y, z, X, M¹, M², R¹, and R²are as defined previously for formula (I).

In some embodiments of the multifunctional CSA of formula (I), each ofm, n, and q is an integer of 1; each of p, r, s, and t is an integer of1 or 2, that is a multifunctional CSA of formula (Ip):((R¹)_(y)M¹(—CH₂)_(r))_(t))—R^(L)—[(X—)_(s)M²(R²)_(z)]_(p)  (Ip))or an exchange product thereof, and R^(L) is a tetravalent radical of a(C₃-C₁₉)alkane or (C₃-C₁₉)alkene, where one of r and t is 1 and theother of r and t is 2 and one of p and s is 1 and the other of p and sis 2; and y, z, X, M¹, M², R¹, and R² are as defined previously forformula (I).

In some embodiments of the multifunctional CSA of formula (I), R¹ and R²are aprotic, that is R¹ and R² do not contain an —OH, —NH, —PH, or —SHmoiety.

In some embodiments of the multifunctional CSA of formula (IA), each ofm, n and p is an integer of 1, and R^(L) is a (C₁-C₁₉)alkylene, suchembodiments being a multifunctional CSA of formula (Ia):(R¹)_(y)M¹-CH₂—(C₁-C₁₉)alkylene-X-M²(R²)_(z)  (Ia)or an exchange product thereof, wherein R¹, y, M¹, X, M², R², and z areas defined for the compound of formula (IA).

Preferred is the multifunctional CSA of formula (Ia) wherein y is 2, zis 2, X is O, and each of M¹ and M² is Al in a formal oxidation state of+3 as shown in formula (Ia-1):

Preferred is the multifunctional CSA of formula (Ia) wherein y is 2, zis 2, X is N((C₁-C₈)alkyl), and each of M¹ and M² is Al in a formaloxidation state of +3 as shown in formula (Ia-2):

In some embodiments of the multifunctional CSA of formula (IA), n is aninteger of 1, 2, or 3, each of m and p is an integer of 1, and R^(L) isa (C₁-C₁₉)alkylene, such embodiments being a multifunctional CSA offormula (Ib)(R¹)_(y)M¹-[CH₂—(C₁-C₁₉)alkylene-X-M²(R²)_(z)]_(n)  (Ib)wherein R¹, y, M¹, X, M², R², and z are as defined for the compound offormula (IA).

Preferred is the multifunctional CSA of formula (Ib) wherein n is 3, yis 0 (thus R¹ is absent), z is 2, each X is O, each R^(L) independentlyis a (C₁-C₁₉)alkylene, and each of M¹ and M² is Al in a formal oxidationstate of +3 as shown in formula (Ib-1):

Preferred is the multifunctional CSA of formula (Ib) wherein n is 2, Yis 0 (thus R¹ is absent), z is 2, each X is O, each R^(L) independentlyis a (C₁-C₁₉)alkylene, M¹ is Zn in a formal oxidation state of +2, andM² is Al in a formal oxidation state of +3 as shown in formula (Ib-2):

In some embodiments of the multifunctional CSA of formula (IA), p is 2,each of m and n is an integer of 1, and R^(L) is a trivalent radical ofa (C₃-C₆)alkane(R¹)_(y)M¹-CH₂—((C₃-C₁₉)alkan-triyl)-[X-M²(R²)_(z)]₂  (Ic)or an exchange product thereof, wherein R¹, y, M¹, X, M², R², and z areas defined for the compound of formula (IA).

Preferred is the multifunctional CSA of formula (Ic) wherein Y is 2,each z is 2, each X is O, R^(L) is a trivalent radical of a(C₃-C₁₉)alkane, and each of M¹ and M² is Al in a formal oxidation stateof +3 as shown in formula (Ic-1):

Preferred is the multifunctional CSA of formula (Ic-1) as shown informula (Ic-1a):

In some embodiments of the multifunctional CSA of formula (IA), m is aninteger of 1, 2, 3, or 4, each of n and p is an integer of 1, and R^(L)is a (C₁-C₁₉)alkylene, such embodiments being a multifunctional CSA offormula (Id):{(R¹)_(y)M¹-CH₂—(C₁-C₁₉)alkylene-X—}_(m)M²(R²)_(z)  (Id)or an exchange product thereof, wherein R¹, y, M¹, X, M², R², and z areas defined for the compound of formula (IA).

Preferred is the multifunctional CSA of formula (Id) wherein m is 3,each y is 2, z is 0 (thus R² is absent), each X is O, each R^(L)independently is (C₁-C₁₉)alkylene, and each of M¹ and M² is Al in aformal oxidation state of +3 as shown in formula (Id-1):

In some embodiments of the multifunctional CSA of formula (IA), each ofm, n and p is an integer of 1, and R^(L) is a (C₂-C₁₉)alkenylene, suchembodiments being a multifunctional CSA of formula (Ie):(R¹)_(y)M¹-CH₂—(C₂-C₁₉)alkenylene-X-M²(R²)_(z)  (Ie)or an exchange product thereof, wherein R¹, y, M¹, X, M², R², and z areas defined for the compound of formula (IA).

Preferred is the multifunctional CSA of formula (Ie) wherein y is 2, zis 2, X is O, and each of M¹ and M² is Al in a formal oxidation state of+3 as shown in formula (Ie-1):

Preferred is the multifunctional CSA of formula (Ia) wherein y is 2, zis 2, X is N((C₁-C₈)alkyl), and each of M¹ and M² is Al in a formaloxidation state of +3 as shown in formula (Ie-2):

In some embodiments of the multifunctional CSA of formula (IA), each ofm, n, and p is 1, (R¹)_(y)M¹ is absent, and M² is taken together withthe CH₂ in formula (IA) to form the multifunctional chain shuttlingagent of formula (II):

or an exchange product thereof, wherein g is an integer of 0, 1, or 2and is chosen such that the sum of (g+2q) is equal to the formaloxidation state of M²; and R^(L), X, M², and R² are as defined for thecompound of formula (IA).Preferred is the multifunctional CSA of formula (II) wherein g is 1, qis 1, R^(L) is (CH₂)₁₋₆, X is O, and M² is Al in a formal oxidationstate of +3 as shown in formula (IIa):

Also preferred is the multifunctional CSA of any one of formulas (I),(IA), (Ia), (Ia-1), (Ib), (Ib-1), (Ib-2), (Ic), (Ic-1), (Id), (Id-1),(Ie), (Ie-1), (II), or (IIa), or an exchange product thereof, whereininstead of each X is O, at least one, and more preferably each X isN((C₁-C₆)alkyl) and any remaining X is as defined for formula (I). Alsopreferred is the multifunctional CSA of any one of formulas (I), (IA),(Ia), (Ia-1), (Ib), (Ib-1), (Ib-2), (Ic), (Ic-1), (Id), (Id-1), (Ie),(Ie-1), (II), or (IIa), or an exchange product thereof, wherein insteadof each X is O, at least one, and more preferably each X is S, N(H),P(H), or P((C₁-C₂₀)hydrocarbyl), and any remaining X is as defined forformula (I).

In some embodiments of the multifunctional CSA of formula (I) (and thusany subgeneric formula such as, for example, (IA), (Ia), (Ia-1), (Ia-2),(Ib), (Ib-1), (Ib-2), (Ic), (Ic-1), (Id), (Id-1), (Ie), (Ie-1), (Ie-2),and (IIa)), certain R^(L), X, R¹, R², M¹, M², m, n, p, q, r, s, t, y,and z are preferred.

Preferably M¹ and M² independently are a metal of Group 2 that ismagnesium (Mg) or calcium (Ca), the Mg or Ca being in a formal oxidationstate of +2; tin (Sn), the Sn being in a formal oxidation state of +2 or+4; a metal of Group 12 that is zinc (Zn), the Zn being in a formaloxidation state of +2; or a metal of Group 13 that is boron (B),aluminum (Al), or gallium (Ga), the B, Al, or Ga being in a formaloxidation state of +3.

More preferably, each M¹ independently is Al, B, or Ga, the Al, B, or Gabeing in a formal oxidation state of +3; or Zn or Mg, the Zn or Mg beingin a formal oxidation state of +2. In some embodiments, each M¹independently is Al, B, or Ga, the Al, B, or Ga being in a formaloxidation state of +3. In some embodiments, each M¹ is Al in a formaloxidation state of +3. In some embodiments, each M¹ independently is Znor Mg in a formal oxidation state of +2. In some embodiments, each M¹ isZn in a formal oxidation state of +2.

Also more preferably, each M² is Al, the Al being in a formal oxidationstate of +3; or Zn, the Zn being in a formal oxidation state of +2; orSn, the Sn being in a formal oxidation state of +2 or +4. In someembodiments, each M² is Al in a formal oxidation state of +3. In someembodiments, each M² independently is Zn in a formal oxidation state of+2. In some embodiments, each M² independently is Sn in a formaloxidation state of +2 or +4.

In some embodiments, each M¹ and M² is Al in a formal oxidation state of+3. In some embodiments, each M¹ and M² is Zn in a formal oxidationstate of +2.

In some embodiments, each (CH₂)₂₋₂₀, (C₁-C₁₉)alkylene,(C₂-C₁₉)alkenylene, trivalent radical of a (C₃-C₁₉)alkane, or trivalentradical of a (C₃-C₁₉)alkene for R^(L) independently is a (CH₂)₂₋₁₂,(C₁-C₁₂)alkylene, (C₂-C₁₂)alkenylene, a trivalent radical of a(C₃-C₁₂)alkane, or a trivalent radical of a (C₂-C₁₂)alkene,respectively; more preferably, a (CH₂)₂₋₁₀, (C₁-C₁₀)alkylene,(C₂-C₁₀)alkenylene, a trivalent radical of a (C₃-C₁₀)alkane, or atrivalent radical of a (C₂-C₁₀)alkene, respectively; and still morepreferably a (CH₂)₂₋₈, (C₁-C₈)alkylene, (C₂-C₈)alkenylene, a trivalentradical of a (C₃-C₈)alkane, or a trivalent radical of a (C₂-C₈)alkene,respectively.

In some embodiments, each (C₁-C₈)alkylene is an unbranched(C₁-C₈)alkylene. In some embodiments, each unbranched (C₁-C₈)alkyleneindependently is CH₂, CH₂CH₂, or (CH₂)₃. In some embodiments, theunbranched (C₁-C₈)alkylene independently is (CH₂)₃. In some embodiments,the unbranched (C₁-C₈)alkylene independently is (CH₂)₄, (CH₂)₅, or(CH₂)₆. In some embodiments, the unbranched (C₁-C₈)alkyleneindependently is (CH₂)₈. In some embodiments, each (C₁-C₈)alkylene is(C₁ or C₂)alkylene (i.e., CH₂ or CH₂CH₂).

In some embodiments, at least one (C₁-C₈)alkylene is a branched(C₃-C₈)alkylene.

In some embodiments, the trivalent radical of (C₃-C₈)alkane is atrivalent radical of a (C₆)alkane. In some embodiments, the trivalentradical of (C₃-C₈)alkane is a trivalent radical of a (C₅)alkane. In someembodiments, the trivalent radical of (C₃-C₈)alkane is a trivalentradical of a (C₄)alkane. In some embodiments, the trivalent radical of(C₃-C₈)alkane is a trivalent radical of a (C₃)alkane. The trivalentradical of the (C₆)alkane is more preferred.

In some embodiments, each (C₂-C₈)alkenylene is an unbranched(C₂-C₈)alkenylene. In some embodiments, each unbranched(C₂-C₈)alkenylene is —(CH₂)₅—C(H)═C(H)—CH₂—.

In some embodiments, each R² independently is a (C₁-C₄₀)hydrocarbyl, andmore preferably (C₁-C₂₀)hydrocarbyl. In some embodiments, each R²independently is a —C(═O)—(C₁-C₂₀)hydrocarbyl (e.g., acetyl, propionyl,or hexanoyl). In some embodiments, z is 2 or 3 and two R² are takentogether to form a (C₂-C₂₀)hydrocarbylene.

In some embodiments, at least one (C₁-C₄₀)hydrocarbyl is (C₁-C₄₀)alkyl.In some embodiments, R¹ is a (C₁-C₂₀)alkyl. In some embodiments, R² is a(C₁-C₂₀)alkyl. In some embodiments, each of R¹ and R² independently is a(C₁-C₂₀)alkyl. In some embodiments, each (C₁-C₄₀)hydrocarbyl is(C₁-C₂₀)alkyl. In some embodiments, each (C₁-C₂₀)alkll independently isa (C₁-C₁₀)alkyl, more preferably a (C₂-C₈)alkyl, and still morepreferably a (C₃-C₆)alkyl. In some embodiments, y is 2, one R¹ is(C₁-C₂₀)hydrocarbyl, and one R¹ is (R³)₂N—, (R³)₂P—, R³S—, or R³O—. Insome embodiments, y is 2 and two R¹ are taken together to form a(C₂-C₂₀)hydrocarbylene.

In some embodiments, R³ is a (C₁-C₂₀)hydrocarbyl. In some embodiments,R³ is ((C₁-C₂₀)hydrocarbyl)₃Si—.

In some embodiments, each X is N(H). In some embodiments, each X is S.In some embodiments, each X is P(H). In some embodiments, each X isP((C₁-C₂₀)hydrocarbyl). In some embodiments, and more preferably, each Xis O. In some embodiments, and more preferably, each X isN((C₁-C₂₀)hydrocarbyl). In some embodiments, each (C₁-C₂₀)hydrocarbyl is(C₁-C₂₀)alkyl. In some embodiments, (C₁-C₂₀)alkyl is (C₁-C₁₂)alkyl.

In some embodiments, each of the aforementioned (C₁-C₁₉)alkylene,(C₂-C₁₉)alkenylene, (C₃-C₁₉)alkane, (C₃-C₁₉)alkene, (C₁-C₂₀)hydrocarbyl,and (C₂-C₂₀)hydrocarbylene are unsubstituted (i.e., all groups in themultifunctional CSA of formula (I) are unsubstituted). In someembodiments, at least one of the aforementioned (C₁-C₁₉)alkylene,(C₂-C₁₉)alkenylene, (C₃-C₁₉)alkane, (C₃-C₁₉)alkene, (C₁-C₂₀)hydrocarbyl,and (C₂-C₂₀)hydrocarbylene is substituted with one or more substituentsR^(s), preferably 1 or 2 R^(s). In some embodiments, each R^(s)independently is fluoro, unsubstituted (C₁-C₁₈)alkyl, or unsubstituted(C₁-C₉)heteroaryl, more preferably unsubstituted (C₁-C₁₀)alkyl, orunsubstituted (C₁-C₉)heteroaryl. Preferably, the unsubstituted(C₁-C₉)heteroaryl is pyridinyl.

In some embodiments, polymerizable olefins (i.e., olefin monomers andolefin comonomers) useful in the invention processes are(C₂-C₄₀)hydrocarbons consisting of carbon and hydrogen atoms andcontaining at least 1 and preferably no more than 3, and more preferablyno more than 2 carbon-carbon double bonds, where the carbon-carbondouble bonds do not include aromatic carbon-carbon bonds (e.g., as inphenyl). In some embodiments, from 1 to 4 hydrogen atoms of the(C₂-C₄₀)hydrocarbons are replaced, each by a halogen atom, preferablyfluoro or chloro to give halo-substituted (C₂-C₄₀)hydrocarbons. The(C₂-C₄₀)hydrocarbons (not halo-substituted) are preferred. Preferredpolymerizable olefins (i.e., olefin monomers) useful for making thepolyolefins are ethylene and polymerizable (C₃-C₄₀)olefins. The(C₃-C₄₀)olefins include an alpha-olefin, a cyclic olefin, styrene, and acyclic or acyclic diene. Preferably, the alpha-olefin comprises a(C₃-C₄₀)alpha-olefin, more preferably a branched chain(C₃-C₄₀)alpha-olefin, still more preferably a linear-chain(C₃-C₄₀)alpha-olefin, even more preferably a linear chain(C₃-C₄₀)alpha-olefin of formula (A): CH₂═CH₂—(CH₂)_(k)CH₃ (A), wherein kis an integer of from 0 to 37, and yet even more preferably alinear-chain (C₃-C₄₀)alpha-olefin that is 1-propene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, a (C₈-C₄₀)alpha-olefin, or alinear chain (C₂₀-C₂₄)alpha-olefin. Another preferred polyolefin is a(C₈-C₄₀)olefin that is non-aromatic or aromatic, the aromatic(C₈-C₄₀)olefin containing at least one derivative of benzene (e.g.,styrene, alpha-methylstyrene or divinylbenzene) or naphthalene (e.g.,vinyl-naphthalene). Similarly as mentioned above, the (C₈-C₄₀)olefin canbe optionally substituted to give a halo-substituted (C₈-C₄₀)olefin(e.g., 4-fluorostyrene). Preferably the cyclic olefin is a(C₃-C₄₀)cyclic olefin. Preferably, the cyclic or acyclic diene is a(C₄-C₄₀)diene, preferably an acyclic diene, more preferably an acyclicconjugated (C₄-C₄₀)diene, more preferably an acyclic 1,3-conjugated(C₄-C₄₀)diene, and still more preferably 1,3-butadiene.

Polyolefins (e.g., homopolymeric polyolefins, telechelic polyolefins,and end functional polyolefins) that can be made by the inventionprocess include, for example, olefin homopolymers comprising residualsof one of the olefin monomers described in the immediately precedingparagraph. Examples of the polyolefin homopolymers are polyethylene,polypropylene, poly(C₃-C₄₀)alpha-olefins, and polystyrene. Otherpolyolefins that can be made by the invention process include, forexample, olefin interpolymers, including olefin copolymers, especiallyolefin block copolymers, and telechelic olefin interpolymers. In someembodiments are olefin interpolymers that comprise residuals of ethyleneand one or more polymerizable (C₃-C₄₀)olefins such as, for example, apoly(olefin monomer-olefin comonomer) block copolymer. Preferredpolymerizable (C₃-C₄₀)olefins are (C₃-C₄₀)alpha-olefins. Preferredolefin interpolymers are those prepared by co-polymerizing a mixture oftwo or more polymerizable olefins such as, for example,ethylene/propylene, ethylene/1-butene, ethylene/1-pentene,ethylene/1-hexene, ethylene/4-methyl-1-pentene, ethylene/1-octene,ethylene/styrene, ethylene/propylene/butadiene,ethylene/propylene/hexadiene, ethylene/propylene/ethylidenenorbornene,and other EPDM terpolymers. Preferably, the polyolefin is an ethylenehomopolymer (e.g., a high density polyethylene), anethylene/alpha-olefin interpolymer (i.e., poly(ethylene alpha-olefin)copolymer such as, for example, a poly(ethylene 1-octene)), or anethylene/alpha-olefin/diene interpolymer (i.e., a poly(ethylenealpha-olefin diene)terpolymer such as, for example, a poly(ethylene1-octene 1,3-butadiene). The polyolefins include non-block poly(olefinmonomer-olefin comonomer) copolymers.

In some embodiments, the invention polyolefin comprises a blend of atleast two different polyolefins, at least one of which can be made bythe invention process. Examples of such blends include a blend ofpolypropylene homopolymer and an invention poly(olefin monomer-olefincomonomer) block copolymer.

In some embodiments, the invention poly(olefin monomer-olefin comonomer)block copolymer can be represented by the following formula:A-B or A-B-Awhere “A” represents a hard block or segment and “B” represents a softblock or segment. Preferably, As and Bs are linked in a linear fashion,not in a branched or a star fashion.

Other embodiments of the invention can be represented by the followingformula:A-[(BA)_(n)] or A-[(BA)_(n)B]

where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a linear fashion, not in abranched or a star fashion.

Further embodiments of the invention can be represented by the followingformula:A-(AB)_(n)-A or A-(AB)_(n)—B or B-(AB)_(n)—Bwhere n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a linear fashion, not in abranched or a star fashion.

In other embodiments, the invention poly(olefin monomer-olefincomonomer) block copolymers usually do not have a third type of block.In still other embodiments, each of block A and block B has monomers orcomonomers randomly distributed within the block. In other words,neither block A nor block B comprises two or more segments (orsub-blocks) of distinct composition, such as a tip segment, which has adifferent composition than the rest of the block.

In other embodiments, the invention poly(olefin monomer-olefincomonomer) block copolymers do have a third type of block or segment andcan be represented by the following formula:A-B—Cwhere “A” represents a hard block or segment, “B” represents a softblock or segment, and “C” represents either a hard or soft block orsegment. Preferably, As, Bs, and Cs are linked in a linear fashion, notin a branched or a star fashion.

Other embodiments of the invention can be represented by the followingformula:A-(BC)_(n) or A-(BC)_(n)B or A-(CB)_(n) or A-(CB)_(n)Cwhere n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment, “B” represents a soft block orsegment, and “C” represents either a hard or soft block or segment.Preferably, As, Bs, and Cs are linked in a linear fashion, not in abranched or a star fashion.

Further embodiments of the invention can be represented by the followingformula:A-(BC)_(n)-A or A-(BC)_(n)—B or A-(BC)_(n)—Cor B-(AC)_(n)-A or B-(AC)_(n)—B or B-(AC)_(n)—Cor C-(AB)_(n)-A or C-(AB)_(n)—B or C-(AB)_(n)—Cwhere n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment, “B” represents a soft block orsegment, and “C” represents either a hard or soft block or segment.Preferably, As and Bs are linked in a linear fashion, not in a branchedor a star fashion.

“Hard” blocks or segments refer to crystalline or semi-crystallineblocks of polymerized units in which in some embodiments containethylene, preferably ethylene is present in an amount greater than about80 mole percent, and preferably greater than 88 mole percent. In otherwords, the comonomer content in the hard segments is less than 20 molepercent, and preferably less than 12 weight percent. In someembodiments, the hard segments comprise all or substantially allethylene. Such hard blocks are sometimes referred to herein as “richpolyethylene” blocks or segments.

“Soft” blocks or segments, on the other hand, refer to blocks ofpolymerized units in which the comonomer content is greater than 20 molepercent, preferably greater than 25 mole percent, up to 100 molepercent. In some embodiments, the comonomer content in the soft segmentscan be greater than 20 mole percent, greater than 25 mole percent,greater than 30 mole percent, greater than 35 mole percent, greater than40 mole percent, greater than 45 mole percent, greater than 50 molepercent, or greater than 60 mole percent. “Soft” blocks or segments mayrefer to amorphous blocks or segments or with levels of crystallinitylower than that of the “hard” blocks or segments.

Additional embodiments include the invention poly(olefin monomer-olefincomonomer) block copolymers wherein at least one of the polymer blocksis amorphous (“soft” block”) and at least one other polymer block iscrystallizable (“hard” block). Preferably the difference between theexpected T_(g) (glass transition temperature, as measured byDifferential Scanning calorimetry (DSC)) for the amorphous polymer blockand T_(m) (melt transition temperature, as measured by DSC) for thecrystallizable polymer block is at least 40° C., more preferably atleast 80° C., and still more preferably at least 100° C. Crystallinemelting point (Tm) refers to the peak melting point determined by DSCaccording to ASTM D-3418 test method. Preferably, T_(m) for thecrystallizable polymer block is higher than the expected T_(g) for theamorphous polymer block. More preferably, at least one block iscrystalline or semicrystalline, having a crystalline melting point of atleast 100° C., still more preferably at least 105° C., and even morepreferably at least 120° C.; and at least one block is amorphous ornon-crystalline. Also preferably, the heat of fusion associated with themelting point of any crystalline polymer block is at least 20 Joules pergram (J/g), preferably at least 40 J/g, and more preferably at least 50J/g, as determined by DSC analysis. DSC analysis is according to thestandard method described later. The invention also includes polymers inwhich crystallinity is induced or enhanced by the use of nucleatingagents, thermal annealing, and/or strain. As used herein the term“expected” when used in reference to the properties of polymer entitiesare those properties predicted by the method for infinite molecularweight, room temperature (25° C.), atactic, polymer calculationdisclosed in Jozef Bicerano, Prediction of Polymer Properties, 2nd ed.,Marcel Dekker, Inc., New York (Bicerano technique). The technique isalso incorporated into software, including SYNTHIA™, available fromMolecular Simulations Inc., a subsidiary of Pharmacopeia, Inc. Theexpected properties of certain representative polymers calculatedaccording to the Bicerano technique are found in Table 1 in WO2008/027283 and corresponding U.S. patent application Ser. No.12/377,034, filed Feb. 10, 2009. In some embodiments, the hard segmentsor blocks comprise all or at least 90 mole percent of an alpha-olefin.Such hard blocks may be referred to herein as “rich poly(alpha-olefin)”blocks or segments. The alpha-olefin comprising the hard richpoly(alpha-olefin) block may be, for example, polypropylene,poly(1-butene), or poly(4-methyl-1-pentene.

Preferred polyolefins include copolymers (e.g., ethylene/octenecopolymers) having trade names ATTANE™ and AFFINITY™, and ENGAGE™polyolefin elastomers, each available from The Dow Chemical Company,Michigan, USA; and olefin copolymers (e.g., ethylene/1-butenecopolymers) made using INSITE® technology of The Dow Chemical Company.

The composition of formula (IVa), telechelic poly(olefin monomer-olefincomonomer) multiblock copolymer, poly(olefin monomer-olefin comonomer)multiblock copolymer, poly(olefin monomer-olefin comonomer)/polyestermultiblock interpolymer poly(olefin monomer-olefin comonomer)/polyethermultiblock interpolymer, poly(olefin monomer-olefin comonomer)/polyamidemultiblock interpolymer, and poly(olefin monomer-olefincomonomer)/polyisocyanate multiblock interpolymer each comprise at leasta portion that is a poly(olefin monomer-olefin comonomer). Thepoly(olefin monomer-olefin comonomer) comprises a plurality of repeatunits, each repeat unit independently being a residual of the olefinmonomer or comonomer, or a derivative of the residual of the olefinmonomer or comonomer, the plurality of repeat units of the poly(olefinmonomer-olefin comonomer) comprising a rich poly(olefin monomer) segment(i.e., comprising more residuals of the olefin monomer than residuals ofthe olefin comonomer, if any) and a different poly(olefin comonomer)segment (i.e., comprising a higher mole percent of residuals of theolefin comonomer than mole percent of residuals of the olefin comonomer,if any, in the poly(olefin monomer) segment).

Preferred invention poly(olefin monomer-olefin comonomer) ischaracterizable as being a multiblock interpolymer having blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties, and characterizable as being mesophaseseparated. Such polymers are sometimes referred to herein as“mesophase-separated olefin multiblock interpolymers.” Preferably, eachpoly(olefin monomer-olefin comonomer) independently is characterizableas being mesophase separated and having a PDI of 1.4 or greater.

More preferably, each poly(olefin monomer-olefin comonomer)independently is a poly(ethylene alpha-olefin). The poly(ethylenealpha-olefin) comprises an ethylene-derived hard segment and a softsegment comprising residuals from the alpha-olefin and ethylene. Wherepoly(ethylene alpha-olefin) comprises a rich polyethylene segment,crystallization of such rich polyethylene segment is primarilyconstrained to resulting mesodomains and such poly(ethylenealpha-olefin) may be referred to as “mesophase separated.”

Preferably, the poly(ethylene alpha-olefin) independently ischaracterizable as being mesophase separated and having a PDI of from1.4 to 8. Preferably, each such PDI is characterizable as fitting aSchutz-Flory distribution rather than a Poisson distribution.Preferably, each poly(ethylene alpha-olefin) independently ischaracterizable as having both a polydisperse block distribution as wellas a polydisperse distribution of block sizes, which characteristicsimpart improved and distinguishable physical properties thereto. Alsopreferably, each poly(ethylene alpha-olefin) independently ischaracterizable as having a difference in mole percent of alpha-olefincontent between the polyethylene and other blocks.

As used herein, the term “mesophase separation” means a process in whichpolymeric blocks are locally segregated to form ordered domains. Thesemesodomains can take the form of spheres, cylinders, lamellae, or anyother morphology known for block copolymers.

Sizes of domains of the mesophase-separated olefin multiblockinterpolymer can be controlled by varying molecular weight of themesophase-separated olefin multiblock interpolymer or changing thedifference in comonomer content of the mesophase-separated olefinmultiblock interpolymer. Sizes of the domains can also be modified byblending a blend component with bulk mesophase-separated olefinmultiblock interpolymer. Examples of suitable blend components includehomopolymer or copolymer with similar composition as one of therespective blocks or segments of the mesophase-separated olefinmultiblock interpolymer, an oil such as mineral oil, and a solvent (usedas a diluent) such as toluene or hexane.

In some embodiments, the domains of the mesophase-separated olefinmultiblock interpolymer are characterizable as having a size that is atleast 50% larger than domain sizes in conventional monodisperse (i.e.,PDI less than 2, e.g., PDI about 1) block copolymers. Sizes of thedomains can be controlled by varying the molecular weight of themesophase-separated olefin multiblock interpolymers or changingcomonomer content thereof such that at least two blocks (i.e., the hardand soft segments) of the mesophase-separated olefin multiblockinterpolymer differ thereby. The desired amounts of comonomer may bemeasured in mole percent. A calculation may be made for any desiredcomonomer in order to determine the amount required to achieve mesophaseseparation.

Domain sizes of the mesophase-separated olefin multiblock interpolymerare typically in the range of from about 40 nanometers (nm) to about 300nm. The mesophase-separated olefin multiblock interpolymers compriseolefin block copolymers wherein the amount of comonomer in the softsegments as compared to that in the hard segments is such that themesophase-separated olefin multiblock interpolymer undergoes mesophaseseparation in a melt thereof.

In some embodiments, the polyolefin comprises an ethylene/alpha-olefininterpolymer, such as those described in PCT International PatentApplication Publication Number WO 2009/097560, which is hereinincorporated by reference, preferably a block copolymer, which comprisesa hard segment and a soft segment, and is characterized by a M_(w)/M_(n)in the range of from about 1.4 to about 2.8 and:

-   -   (a) has at least one T_(m) (° C.), and a density (d) in        grams/cubic centimeter, wherein the numerical values of T_(m)        and d correspond to the relationship:        T _(m)>−6553.3+13735(d)−7051.7(d)², or    -   (b) is characterized by a heat of fusion (ΔH, in J/g), and a        delta temperature quantity (ΔT, in ° C.), defined as the        temperature difference between the tallest differential scanning        calorimetry (DSC) peak and the tallest crystallization analysis        fractionation (CRYSTAF) peak, wherein the numerical values of ΔT        and ΔH have the following relationships:        ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero (0) and up to 130        J/g,        ΔT≧48° C. for ΔH greater than 130 J/g,        wherein the CRYSTAF peak is determined using at least 5 percent        of the cumulative polymer, and if less than 5 percent of the        polymer has an identifiable CRYSTAF peak, then the CRYSTAF        temperature is 30° C.; or    -   (c) is characterized by an elastic recovery (R_(e)) in percent        at 300 percent strain and 1 cycle measured with a        compression-molded film of the ethylene/alpha-olefin        interpolymer, and has a density d in grams/cubic centimeter,        wherein the numerical values of R_(e) and d satisfy the        following relationship when ethylene/alpha-olefin interpolymer        is substantially free of a cross-linked phase:        R_(e)>1481−1629(d); or    -   (d) has a molecular fraction which elutes between 40° C. and        130° C. when fractionated using TREF, characterized in that the        fraction has a molar comonomer content of at least 5 percent        higher than that of a comparable random ethylene interpolymer        fraction eluting between the same temperatures, wherein said        comparable random ethylene interpolymer has the same        comonomer(s) and has a melt index, density, and molar comonomer        content (based on the whole polymer) within 10 percent of that        of the ethylene/alpha-olefin interpolymer; or    -   (e) has a storage modulus at 25° C. (G′(25° C.)) and a storage        modulus at 100° C. (G′ (100° C.)) wherein the ratio of G′(25°        C.) to G′(100° C.) is in the range of about 1:1 to about 9:1; or    -   (f) is characterized by an average block index greater than        zero (0) and up to about 1.0; or    -   (g) has a molecular fraction which elutes between 40° C. and        130° C. when fractionated using TREF, characterized in that the        fraction has a molar comonomer content greater than, or equal        to, the quantity (−0.2013) T+20.07, more preferably greater than        or equal to the quantity (−0.2013) T+21.07, where T is the        numerical value of the peak elution temperature of the TREF        fraction, measured in ° C.; and,        wherein the ethylene/alpha-olefin block interpolymer is        mesophase separated.

In some embodiments, the polyolefin comprises an ethylene/alpha-olefininterpolymer, such as that described in U.S. Pat. No. 7,355,089 and U.S.Patent Application Publication No. US 2006-0199930, wherein theinterpolymer is preferably a block copolymer, and comprises a hardsegment and a soft segment, and the ethylene/alpha-olefin interpolymer:

(a) has an M_(w)/M_(n) from about 1.7 to about 3.5, at least one T_(m)(° C.), and a density d, in grams/cubic centimeter, wherein thenumerical values of T_(m) and d correspond to the relationship:Tm>−2002.9+4538.5(d)−2422.2(d)₂; or(b) has a M_(w)/M_(n) from about 1.7 to about 3.5, and is characterizedby a heat of fusion, ΔH in J/g, and a delta quantity, ΔT (° C.), definedas the temperature difference between the tallest DSC peak and thetallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have thefollowing relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 μg,ΔT≧48° C. for ΔH greater than 130 μg,wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or(c) is characterized by an R_(e) in percent at 300 percent strain and 1cycle measured with a compression-molded film of theethylene/alpha-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of R_(e) and d satisfy thefollowing relationship when ethylene/alpha-olefin interpolymer issubstantially free of a cross-linked phase:R_(e)>1481−1629(d); or(d) has a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has amolar comonomer content of at least 5 percent higher than that of acomparable random ethylene interpolymer fraction eluting between thesame temperatures, wherein said comparable random ethylene interpolymerhas the same comonomer(s) and has a melt index, density, and molarcomonomer content (based on the whole polymer) within 10 percent of thatof the ethylene/alpha-olefin interpolymer; or(e) has a storage modulus at 25° C. (G′(25° C.)), and a storage modulusat 100° C., (G′(100° C.)), wherein the ratio of G′(25° C.) to G′(100°C.) is in the range of about 1:1 to about 9:1 or(f) has a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has ablock index of at least 0.5 and up to about 1 and a M_(w)/M_(n) greaterthan about 1.3; or(g) has an average block index greater than zero (0) and up to about 1.0and a M_(w)/M_(n) greater than about 1.3; or(h) has a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has amolar comonomer content greater than, or equal to, the quantity(−0.2013) T+20.07, more preferably greater than or equal to the quantity(−0.2013) T+21.07, where T is the numerical value of the peak elutiontemperature of the TREF fraction, measured in ° C.

Other embodiments comprise polymers and processes such as thosedescribed in PCT International Patent Application Publication Nos. WO2005/090425 A1 and its corresponding US 2007/0167315 A1, WO 2005/090426A1 and its corresponding US 2008/0311812 A1, and WO 2005/090427 A2 andits corresponding US 2007/0167578 A1.

In other embodiments, the instant block interpolymers are poly(ethylenealpha-olefin) copolymers and related processes and methods described inPCT International Patent Application Publication Number WO 2009/097565,wherein:

-   (a) the poly(ethylene alpha-olefin) copolymer comprises two or more    substantially homogeneous intramolecular blocks comprising differing    chemical or physical properties and having a difference in mole    percent α-olefin content, said intramolecular blocks characterized    by possessing a most probable molecular weight distribution, wherein    at least one poly(ethylene alpha-olefin) copolymer (i.e.,    ethylene/α-olefin interpolymer) is characterized by a molecular    weight distribution, M_(w)/M_(n), in the range of from about 1.4 to    about 2.8 and by an average block index greater than zero and up to    about 1.0; and, wherein the ethylene/α-olefin block interpolymer is    mesophase separated; or-   (b) the poly(ethylene alpha-olefin) copolymer comprises two or more    substantially homogeneous intramolecular blocks comprising differing    chemical or physical properties and having a difference in mole    percent α-olefin content, said intramolecular segments characterized    by possessing a most probable molecular weight distribution, wherein    the block copolymer has a molecular weight of 1,000 g/mole to    1,000,000 g/mole and is mesophase separated; or-   (c) the poly(ethylene alpha-olefin) copolymer comprises two or more    substantially homogeneous intramolecular blocks comprising differing    chemical or physical properties and having a difference in mole    percent α-olefin content, said intramolecular segments characterized    by possessing a most probable molecular weight distribution wherein    the copolymer is characterized by an average molecular weight of    greater than 40,000 g/mol, a molecular weight distribution, Mw/Mn,    in the range of from about 1.4 to about 2.8, and a difference in    mole percent α-olefin content between the intramolecular blocks of    greater than about 20 mole percent.

Monomer and comonomer content of the polyolefins may be measured usingany suitable technique such as, for example, infrared (IR) spectroscopyand nuclear magnetic resonance (NMR) spectroscopy, with techniques basedon NMR spectroscopy being preferred and carbon-13 NMR spectroscopy beingmore preferred. To use carbon-13 NMR spectroscopy, prepare an analysissample from a polymer sample of the high density polyethylene orpoly(ethylene alpha-olefin) block copolymer by adding approximately 3 gof a 50/50 mixture of tetrachloroethane-d²/orthodichlorobenzene to 0.4 gof the polymer sample in a 10 millimeter (mm) NMR tube. Dissolve andhomogenize the polymer sample by heating the tube and its contents to150° C. Collect carbon-13 NMR spectroscopy data using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a carbon-13 resonance frequency of 100.5 MHz. Acquirethe carbon-13 data using 4000 transients per data file with a 6 secondpulse repetition delay. To achieve minimum signal-to-noise forquantitative analysis, add multiple data files together. The spectralwidth is 25,000 Hz with a minimum file size of 32,000 data points.Analyze the analysis sample at 130° C. in a 10 mm broad band probe.Determine the comonomer incorporation with the carbon-13 data usingRandall's triad method (Randall, J. C.; JMS-Rev. Macromol. Chem. Phys.,C29, 201-317 (1989), which is incorporated by reference herein in itsentirety.

In some embodiments, the amount of olefin comonomer incorporated intothe poly(olefin monomer-olefin comonomer) block copolymer or segmentsthereof is characterized by a comonomer incorporation index. As usedherein, the term, “comonomer incorporation index”, refers to the molepercent of residuals of olefin comonomer incorporated into olefinmonomer/comonomer copolymer, or segment thereof, prepared underrepresentative olefin polymerization conditions. Preferably, the olefinmonomer is ethylene or propylene and the comonomer respectively is an(C₃-C₄₀)alpha-olefin or (C₄-C₄₀)alpha-olefin. The olefin polymerizationconditions are ideally under steady-state, continuous solutionpolymerization conditions in a hydrocarbon diluent at 100° C., 4.5megapascals (MPa) ethylene (or propylene) pressure (reactor pressure),greater than 92 percent (more preferably greater than 95 percent) olefinmonomer conversion, and greater than 0.01 percent olefin comonomerconversion. The selection of catalyst compositions, which include theinvention multifunctional compositions, having the greatest differencein olefin comonomer incorporation indices results in poly(olefinmonomer-olefin comonomer) block copolymers from two or more olefinmonomers having the largest difference in block or segment properties,such as density.

In certain circumstances the comonomer incorporation index may bedetermined directly, for example by the use of NMR spectroscopictechniques described previously or by IR spectroscopy. If NMR or IRspectroscopic techniques cannot be used, then any difference incomonomer incorporation is indirectly determined. For polymers formedfrom multiple monomers this indirect determination may be accomplishedby various techniques based on monomer reactivities.

For copolymers produced by a given catalyst, the relative amounts ofcomonomer and monomer in the copolymer and hence the copolymercomposition is determined by relative rates of reaction of comonomer andmonomer. Mathematically the molar ratio of comonomer to monomer is givenby the equations described in US 2007/0167578 A1, in paragraphs numbered[0081] to [0090].

For this model as well the polymer composition is a function only oftemperature dependent reactivity ratios and comonomer mole fraction inthe reactor. The same is also true when reverse comonomer or monomerinsertion may occur or in the case of the interpolymerization of morethan two monomers.

Reactivity ratios for use in the foregoing models may be predicted usingwell known theoretical techniques or empirically derived from actualpolymerization data. Suitable theoretical techniques are disclosed, forexample, in B. G. Kyle, Chemical and Process Thermodynamics, ThirdAddition, Prentice-Hall, 1999 and in Redlich-Kwong-Soave (RKS) Equationof State, Chemical Engineering Science, 1972, pp 1197-1203. Commerciallyavailable software programs may be used to assist in deriving reactivityratios from experimentally derived data. One example of such software isAspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, Mass.02141-2201 USA.

At times it is convenient to incorporate by reference examples of theoriginal and associate olefin polymerization catalysts. For convenienceand consistency, one of the original and associate olefin polymerizationcatalysts is thus sometimes referred to herein as a “first olefinpolymerization catalyst” and one as a “second olefin polymerizationcatalyst.” That is, in some embodiments, the first olefin polymerizationcatalyst is the same as the original olefin polymerization catalyst andthe second olefin polymerization catalyst is the same as the associateolefin polymerization catalyst; and vice versa in other embodiments. Asused herein, the first olefin polymerization catalyst is characterizableas having a high comonomer incorporation index and the second olefinpolymerization catalyst is characterizable as having a comonomerincorporation index that is less than 95 percent of the high comonomerincorporation index. Preferably, the second olefin polymerizationcatalyst is characterized as having a comonomer incorporation index thatis less than 90 percent, more preferably less than 50 percent, stillmore preferably less than 25 percent, and even more preferably less than10 percent of the high comonomer incorporation index of the first olefinpolymerization catalyst.

In some embodiments, the invention process employs a catalyst systemcomprising a mixture or reaction product of:

-   -   (A) a first olefin polymerization catalyst, the first olefin        polymerization catalyst being characterized as having a high        comonomer incorporation index (e.g., a comonomer incorporation        index of 15 mole percent of comonomer or higher);    -   (B) a second olefin polymerization catalyst, the second olefin        polymerization catalyst being characterized as having a        comonomer incorporation index that is less than 90 percent of        the comonomer incorporation index of the first olefin        polymerization catalyst; and    -   (C) the invention multifunctional chain shuttling agent;        In some embodiments, the original olefin polymerization catalyst        is the first olefin polymerization catalyst and the associate        olefin polymerization catalyst is the second olefin        polymerization catalyst. In some embodiments, the original        olefin polymerization catalyst is the second olefin        polymerization catalyst and the associate olefin polymerization        catalyst is the first olefin polymerization catalyst.

The term “catalyst” as generally used herein may refer to an unactivatedform of a metal-ligand complex (i.e., precursor) or, preferably, theactivated form thereof (e.g., after contact of the unactivated form withan activating cocatalyst to give a catalytically active mixture orproduct thereof). The metal of the metal-ligand complex can be a metalof any one of Groups 3 to 15, preferably Group 4, of the Periodic Tableof the Elements. Examples of types of suitable metal-ligand complexesare metallocene, half-metallocene, constrained geometry, and polyvalentpyridylamine-, polyether-, or other polychelating base complexes. Suchmetal-ligand complexes are described in the WO 2008/027283 andcorresponding U.S. patent application Ser. No. 12/377,034. Othersuitable metal-ligand complexes are those described in U.S. Pat. No.5,064,802; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,296,433; U.S. Pat.No. 5,321,106; U.S. Pat. No. 5,350,723; U.S. Pat. No. 5,425,872; U.S.Pat. No. 5,470,993; U.S. Pat. No. 5,625,087; U.S. Pat. No. 5,721,185;U.S. Pat. No. 5,783,512; U.S. Pat. No. 5,866,704; U.S. Pat. No.5,883,204; U.S. Pat. No. 5,919,983; U.S. Pat. No. 6,015,868; U.S. Pat.No. 6,034,022; U.S. Pat. No. 6,103,657; U.S. Pat. No. 6,150,297; U.S.Pat. No. 6,268,444; U.S. Pat. No. 6,320,005; U.S. Pat. No. 6,515,155;U.S. Pat. No. 6,555,634; U.S. Pat. No. 6,696,379; U.S. Pat. No.7,163,907; and U.S. Pat. No. 7,355,089, as well as in applications WO02/02577; WO 02/92610; WO 02/38628; WO 03/40195; WO 03/78480; WO03/78483; WO 2009/012215 A2; US 2003/0004286; and US 04/0220050; US2006/0199930 A1; US 2007/0167578 A1; and US 2008/0311812 A1.

Also for convenience and consistency, the “first olefin polymerizationcatalyst” is interchangeably referred to herein as “Catalyst (A).” The“second olefin polymerization catalyst” is interchangeably referred toherein as “Catalyst (B).” The first and second olefin polymerizationcatalysts preferably have different ethylene and (C₃-C₄₀)alpha-olefinselectivities.

Preferably, the comonomer incorporation index of Catalyst (B) is lessthan 50 percent and more preferably less than 5 percent of the comonomerincorporation index of Catalyst (A). Preferably, the comonomerincorporation index for Catalyst (A) is greater than 20 mol %, morepreferably greater than 30 mol %, and still more preferably greater than40 mol % incorporation of comonomer.

Preferably the Catalyst (A) of the catalyst system independently is aCatalyst (A) described in US 2006/0199930 A1; US 2007/0167578 A1; US2008/0311812 A1; U.S. Pat. No. 7,355,089 B2; or WO 2009/012215 A2. Alsopreferably the Catalyst (B) of the catalyst system independently is aCatalyst (B) described in US 2006/0199930 A1; US 2007/0167578 A1; US2008/0311812 A1; U.S. Pat. No. 7,355,089 B2; or WO 2009/012215 A2. Morepreferred are the catalysts described in US 2007/0167578 A1, paragraphsnumbered [0138] to [0476].

Representative Catalysts (A) and (B) are the catalysts of formulas (A1)to (A5), (B1), (B2), (C1) to (C3), and (D1):

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740, and having the structure:

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740, and having the structure:

Catalyst (A3) isbis[N,N″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafnium dibenzyl,and having the structure:

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of US-A-2004/0010103, and having the structure:

Catalyst (A5) is[η²-2,6-diisopropyl-N-(2-methyl-3-(octylimino)butan-2-yl)benzeneamide]trimethylhafnium,prepared substantially according to the teachings of WO 2003/051935, andhaving the structure:

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)imino)methyl)(2-oxoyl)zirconiumdibenzyl, and having the structure:

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-imino)methyl)(2-oxoyl)zirconiumdibenzyl, and having the structure:

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl, prepared substantially according to the techniques of U.S.Pat. No. 6,268,444, and having the structure:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl, prepared substantially according to the teachings ofUS-A-2003/004286, and having the structure:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl, prepared substantially according to the teachings ofUS-A-2003/004286, and having the structure:

and

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride, available from Sigma-Aldrich, and having the structure:

In some embodiments, the original and associate olefin polymerizationcatalysts are rendered catalytically active by contacting them to, orreacting them with, a same cocatalyst (sometimes referred to as anactivating cocatalyst or co-catalyst) or by using an activatingtechnique such as those that are known in the art for use with metal(e.g., Group 4) olefin polymerization reactions. For example, someembodiments employing both the original and associate olefinpolymerization catalysts further employ only the original cocatalyst. Inother embodiments, the original cocatalyst is used to activate theoriginal olefin polymerization catalyst and the associate cocatalyst isused to activate associate olefin polymerization catalyst.

Suitable cocatalysts for use herein include alkyl aluminums; polymericor oligomeric alumoxanes (also known as aluminoxanes); neutral Lewisacids; and non-polymeric, non-coordinating, ion-forming compounds(including the use of such compounds under oxidizing conditions). Asuitable activating technique is bulk electrolysis (explained in moredetail hereinafter). Combinations of one or more of the foregoingcocatalysts and techniques are also contemplated. The term “alkylaluminum” means a monoalkyl aluminum dihydride or monoalkylaluminumdihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or atrialkylaluminum. Aluminoxanes and their preparations are known at, forexample, U.S. Pat. No. 6,103,657. Examples of preferred polymeric oroligomeric alumoxanes are methylalumoxane, triisobutylaluminum-modifiedmethylalumoxane, and isobutylalumoxane.

Preferred Lewis acid cocatalysts are Group 13 metal compounds containingfrom 1 to 3 hydrocarbyl substituents as described herein. More preferredGroup 13 metal compounds are tri(hydrocarbyl)-substituted-aluminum ortri(hydrocarbyl)-boron compounds, still more preferred aretri((C₁-C₁₀)alkyl)aluminum or tri((C₆-C₁₈)aryl)boron compounds andhalogenated (including perhalogenated) derivatives thereof, even moreespecially tris(fluoro-substituted phenyl)boranes, still even moreespecially tris(pentafluorophenyl)borane. In some embodiments, thecocatalyst is a tris((C₁-C₂₀)hydrocarbyl)borate (e.g., trityltetrafluoroborate) or a tri((C₁-C₂₀)hydrocarbyl)ammoniumtetra((C₁-C₂₀)hydrocarbyl)borane (e.g., bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium”means a nitrogen cation that is a ((C₁-C₂₀)hydrocarbyl)₄N⁺, a((C₁-C₂₀)hydrocarbyl)₃N(H)⁺, a ((C₁-C₂₀)hydrocarbyl)₂N(H)₂ ⁺,(C₁-C₂₀)hydrocarbylN(H)₃ ⁺, or N(H)₄ ⁺, wherein each (C₁-C₂₀)hydrocarbylmay be the same or different.

Preferred combinations of neutral Lewis acid cocatalysts includemixtures comprising a combination of a tri((C₁-C₄)alkyl)aluminum and ahalogenated tri((C₆-C₁₈)aryl)boron compound, especially atris(pentafluorophenyl)borane. Also preferred are combinations of suchneutral Lewis acid mixtures with a polymeric or oligomeric alumoxane,and combinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane.Preferred ratios of numbers of moles of (metal-ligandcomplex):(tris(pentafluoro-phenylborane): (alumoxane) [e.g., (Group 4metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane)] arefrom 1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.

Many cocatalysts and activating techniques have been previously taughtwith respect to different metal-ligand complexes in the following U.S.Pat. No. 5,064,802; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,296,433;U.S. Pat. No. 5,321,106; U.S. Pat. No. 5,350,723; U.S. Pat. No.5,425,872; U.S. Pat. No. 5,625,087; U.S. Pat. No. 5,721,185; U.S. Pat.No. 5,783,512; U.S. Pat. No. 5,883,204; U.S. Pat. No. 5,919,983; U.S.Pat. No. 6,696,379; and U.S. Pat. No. 7,163,907. Examples of suitablehydrocarbyloxides are disclosed in U.S. Pat. No. 5,296,433. Examples ofsuitable Bronsted acid salts for addition polymerization catalysts aredisclosed in U.S. Pat. No. 5,064,802; U.S. Pat. No. 5,919,983; U.S. Pat.No. 5,783,512. Examples of suitable salts of a cationic oxidizing agentand a non-coordinating, compatible anion as cocatalysts for additionpolymerization catalysts are disclosed in U.S. Pat. No. 5,321,106.Examples of suitable carbenium salts as cocatalysts for additionpolymerization catalysts are disclosed in U.S. Pat. No. 5,350,723.Examples of suitable silylium salts as cocatalysts for additionpolymerization catalysts are disclosed in U.S. Pat. No. 5,625,087.Examples of suitable complexes of alcohols, mercaptans, silanols, andoximes with tris(pentafluorophenyl)borane are disclosed in U.S. Pat. No.5,296,433. Some of these catalysts are also described in a portion ofU.S. Pat. No. 6,515,155 B1 beginning at column 50, at line 39, and goingthrough column 56, at line 55, only the portion of which is incorporatedby reference herein.

In some embodiments, one or more of the foregoing cocatalysts are usedin combination with each other. An especially preferred combination is amixture of a tri((C₁-C₄)hydrocarbyl)aluminum,tri((C₁-C₄)hydrocarbyl)borane, or an ammonium borate with an oligomericor polymeric alumoxane compound.

The ratio of total number of moles of the original and associate olefinpolymerization catalysts to total number of moles of one or more of thecocatalysts is from 1:10,000 to 100:1. Preferably, the ratio is at least1:5000, more preferably at least 1:1000; and 10:1 or less, morepreferably 1:1 or less. When an alumoxane alone is used as thecocatalyst, preferably the number of moles of the alumoxane that areemployed is at least 100 times the number of moles of the original andassociate olefin polymerization catalysts. Whentris(pentafluorophenyl)borane alone is used as the cocatalyst,preferably the number of moles of the tris(pentafluorophenyl)borane thatare employed to the total number of moles of one or more original andassociate olefin polymerization catalysts form 0.5:1 to 10:1, morepreferably from 1:1 to 6:1, still more preferably from 1:1 to 5:1. Theremaining cocatalysts are generally employed in approximately molequantities equal to the total mole quantities of one or more originaland associate olefin polymerization catalysts.

The term “catalyst preparing conditions” independently refers toreaction conditions such as solvent(s), atmosphere(s), temperature(s),pressure(s), time(s), and the like that are preferred for giving atleast a 10 percent (%), more preferably at least 20%, and still morepreferably at least 30% reaction yield of the catalyst from the relevantinvention process of after 2 hours reaction time. Preferably, therelevant invention process independently is run under an inertatmosphere (e.g., under an inert gas consisting essentially of, forexample, nitrogen gas, argon gas, helium gas, or a mixture of any two ormore thereof). Preferably, the relevant invention process is run with anaprotic solvent or mixture of two or more aprotic solvents, e.g.,toluene. Preferably, the relevant invention process is run as a reactionmixture comprising the aprotic solvent. The reaction mixture maycomprise additional ingredients such as those described previouslyherein. Preferably, the relevant invention process is run at atemperature of the reaction mixture of from −20° C. to about 200° C. Insome embodiments, the temperature is at least 0° C., and more preferablyat least 20° C. In other embodiments, the temperature is 100° C. orlower, more preferably 50° C. or lower, and still more preferably 40° C.or lower. A convenient temperature is about ambient temperature, i.e.,from about 20° C. to about 30° C. Preferably the relevant inventionprocess independently is run at ambient pressure, i.e., at about 1 atm(e.g., from about 95 kPa to about 107 kPa, such as 101 kPa).

The term “catalytic amount” means mole percent (mol %) of the catalystfor a catalyzed reaction that is less than 100 mol % of a number ofmoles of a product-limiting stoichiometric reactant employed in thecatalyzed reaction and equal to or greater than a minimum mol % valuethat is necessary for at least some product of the catalyzed reaction tobe formed and detected (e.g., by mass spectrometry), wherein 100 mol %is equal to the number of moles of the product-limiting stoichiometricreactant employed in the catalyzed reaction. The minimum catalyticamount preferably is 0.000001 mol %, and may be 0.00001 mol %, 0.0001mol %, 0.001 mol %, or even 0.01 mol %. Preferably, the catalytic amountof each of the olefin polymerization catalysts independently is from0.00001 mol % to 50 mol % of the moles of olefin monomer or comonomer,whichever is lower.

A general process for making polyolefins that can be adapted for makingthe polyolefins of the present invention (e.g., poly(olefinmonomer-olefin comonomer) block copolymers) has been disclosed in PCTPublication No. WO 2007/035485 A1. For example, one such methodcomprises a process for the polymerization of one or more additionpolymerizable monomers, preferably of two or more addition polymerizablemonomers, especially ethylene and at least one copolymerizablecomonomer, propylene and at least one copolymerizable comonomer havingfrom 4 to 20 carbons, or 4-methyl-1-pentene and at least one differentcopolymerizable comonomer having from 4 to 20 carbons, to form acopolymer comprising two regions or segments of differentiated polymercomposition or properties, especially regions comprising differingcomonomer incorporation index, said process comprising:

-   -   contacting an addition polymerizable monomer or mixture of        monomers under addition polymerization conditions, preferably        uniform or homogeneous polymerization conditions, in a reactor        or reactor zone with a composition comprising at least one        olefin polymerization catalyst and at least one cocatalyst and        characterized by the formation of polymer segments from said        monomer or monomers;    -   transferring the reaction mixture to a second reactor or reactor        zone and optionally adding one or more additional reactants,        catalysts, monomers or other compounds prior to,        contemporaneously with, or after said transfer; and    -   causing polymerization to occur in said second reactor or        reactor zone to form polymer segments that are differentiated        from the polymer segments formed in step 1);    -   said process being characterized by addition of a chain        shuttling agent to the reaction mixture prior to, during, or        subsequent to step 1) such that at least some of the resulting        polymer molecules from step 3) comprises two or more chemically        or physically distinguishable blocks or segments. As mentioned        previously, a characteristic of the invention multifunctional        chain shuttling agent is that it comprises a single compound        that is capable of functioning in such a way that at least one        olefin-containing polymeryl chain can be shuttled between two or        more olefin polymerization catalysts. As a test, such polymeryl        chain shuttling preferably is characterized with a process of        preparing a poly(ethylene octene) diblock copolymer, the process        comprising the above listed steps and operated at representative        olefin polymerization conditions (described later herein),        ideally under steady-state, continuous solution polymerization        conditions in a hydrocarbon diluent at 100° C., 4.5 megapascals        (MPa) ethylene pressure (reactor pressure), greater than 92        percent (more preferably greater than 95 percent) ethylene        conversion, and greater than 0.01 percent comonomer (i.e.,        1-octene) conversion. Preferably, the process employs two olefin        polymerization catalysts, one of which being catalyst (A1). The        entire process for producing the block copolymers can also be        carried out in a single reactor.

While the foregoing process has been described for convenience asforming a diblock version of the invention poly(olefin monomer-olefincomonomer) block copolymer, it is an additional object of the inventionto prepare poly(olefin monomer-olefin comonomer) block copolymers having3 or more blocks. The invention poly(olefin monomer-olefin comonomer)block copolymers having 3 or more blocks also includes hyper-branched ordendrimeric copolymers. Such copolymers having 3 or more blocks can beprepared through coupling of the poly(olefin monomer-olefin comonomer)of the poly(olefin monomer-olefin comonomer)-containing multifunctionalchain shuttling agent (e.g., as in the composition of formula (IVa))exiting the second reactor or zone (or any subsequent reactor or zone)using a polyfunctional (e.g., difunctional) coupling agent, the couplingagent being trifunctional or higher for preparing the hyper-branched ordendrimeric copolymers. Further, if more than two reactors are employed,the invention poly(olefin monomer-olefin comonomer) block copolymerhaving three or more blocks resembles what could be made instead byliving polymerization in more than one reactor, with a difference beingthat each block of the former poly(olefin monomer-olefin comonomer)block copolymer having three or more blocks possesses characteristics ofa most probable distribution of molecular weights and composition whilethe blocks of the latter living polymerization product would not possesssuch characteristics. In particular, the polydispersity of the inventionpoly(olefin monomer-olefin comonomer) block copolymer having three ormore blocks is generally less than 2.4 and can approach 1.5 for productmade in two reactors.

In general, the average number of blocks in the absence of thepolyfunctional coupling agent-facilitated coupling of the poly(olefinmonomer-olefin comonomer) block copolymer polymers will be equal to thenumber of reactors employed. The poly(olefin monomer-olefin comonomer)block copolymer products will normally include quantities ofconventional polymer depending on the efficiency of the particularmultifunctional chain shuttling agent (and optionally additional chainshuttling agents, if any) employed under the conditions of thepolymerization.

The invention involves the concept of using multifunctional chainshuttling as a way to prolong the lifetime of (i.e., safekeep) a polymerchain such that a substantial fraction of the polymer chains exit atleast a first reactor of a multiple reactor series or a first reactorzone in a multiple zoned reactor operating substantially under plug flowconditions in the form of polymer chains terminated with themultifunctional chain shuttling agent (e.g., as in the composition offormula (IV) or (IVa)), and the polymer chains experience differentpolymerization conditions in the next reactor or polymerization zone.Different polymerization conditions in the respective reactors or zonesinclude the use of different monomers, comonomers, ormonomer/comonomer(s) ratio, different polymerization temperatures,pressures or partial pressures of various monomers, different catalysts,differing monomer gradients, or any other difference leading toformation of a distinguishable polymer segment. Thus, at least a portionof the polymer resulting from the present process comprises two, three,or more, preferably two or three, differentiated polymer segmentsarranged intramolecularly.

Because the various reactors or zones form a distribution of polymersrather than a single specific polymer composition, the resulting producthas improved properties over a random copolymer or monodisperse blockcopolymer.

As mentioned previously, the poly(olefin monomer-olefin comonomer) blockcopolymers are prepared under olefin polymerizing conditions. Olefinpolymerizing conditions independently refer to reaction conditions suchas solvent(s), atmosphere(s), temperature(s), pressure(s), time(s), andthe like that are preferred for giving at least a 10 percent (%), morepreferably at least 20%, and still more preferably at least 30% reactionyield of the polyolefin or poly(olefin monomer-olefin comonomer) blockcopolymer after 15 minutes reaction time. Preferably, the polymerizationprocesses independently are run under an inert atmosphere (e.g., underan inert gas consisting essentially of, for example, nitrogen gas, argongas, helium gas, or a mixture of any two or more thereof). Otheratmospheres are contemplated, however, and these include sacrificialolefin in the form of a gas and hydrogen gas (e.g., as a polymerizationtermination agent). In some aspects, the polymerization processesindependently are run without any solvent, i.e., is a neatpolymerization process that is run in a neat mixture of aforementionedingredients. In other aspects, the neat mixture further containsadditional ingredients (e.g., catalyst stabilizer such astriphenylphosphine) other than solvent(s). In still other aspects, thepolymerization processes independently are run with a solvent or mixtureof two or more solvents, i.e., is a solvent-based process that is run asa solvent-containing mixture of aforementioned ingredients, and at leastone solvent, e.g., an aprotic solvent. Preferably, the neatpolymerization process or solvent-based polymerization process is run ata temperature of the neat mixture or solvent-containing mixture of from−20° C. to about 250° C., and more preferably from −20° C. to about 200°C. In some embodiments, the temperature is at least 30° C., and morepreferably at least 40° C. In other embodiments, the temperature is 175°C. or lower, more preferably 150° C. or lower, and still more preferably140° C. or lower. A convenient temperature is about 60° C. or about 70°C. In some embodiments, the polymerization processes independently rununder a pressure of about 1000 pounds per square inch (psi) or less,i.e., about 70 atmospheres (atm) or 7000 kilopascals (kPa), or less.Preferably the polymerization processes independently run under apressure of from about 0.9 atm to about 50 atm (i.e., from about 91kiloPascals (kPa) to about 5000 kPa). A convenient pressure is from 3000kPa to 4900 kPa.

In some embodiments, the composition of formula (IV) is prepared insitu, and then used in a subsequent process step as describedpreviously; stored for future use; or isolated and stored for future use(e.g., in a polyester-, polyether, polyamide- or polyisocyanate-formingprocess or as a chain shuttling agent to prepare another composition offormula (IV) or (IVa). Similarly, in some embodiments, the compositionof formula (IVa) is prepared in situ, and then used in a subsequentprocess step as described previously; stored for future use; or isolatedand stored for future use (e.g., in a polyester-, polyether, polyamide-or polyisocyanate-forming process).

In some embodiments, the invention process comprises terminating the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent (e.g., the composition of formula (IV)) to form the polyolefin.The polyolefin is thereby released from the multifunctional chainshuttling agent while leaving terminal functional groups attached to thepolyolefin. Such terminating comprises, for example, contacting the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent to a terminating agent (i.e., quenching) to give the polyolefin(e.g., the poly(olefin monomer-olefin comonomer) block copolymer). Theterminating agent preferably comprises a proton source (e.g., water,aqueous acid, or an alcohol such as 2-propanol). In some embodiments,the terminating agent further comprises a stabilizing agent such as, forexample, an antioxidant (e.g., a hindered phenol antioxidant (IRGANOX™1010 from Ciba Geigy Corporation)), a phosphorous stabilizer (e.g.,IRGAFOS™ 168 from Ciba Geigy Corporation), or both.

Preferably, the invention telechelic polyolefin is characterizable ashaving a non-statistical distribution of the first and second terminalfunctional groups.

In some embodiments, the invention process comprises a step ofterminally functionalizing the polyolefin-polyradical of the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent to form the invention telechelic polyolefin (e.g., the telechelicpoly(olefin monomer-olefin comonomer)). Such terminal functionalizationcomprises conversion of an end (e.g., comprising a carbanion) of thepolyolefin-polyradical into vinyl, hydroxyl, amine, silane, carboxylicacid, carboxylic acid ester, ionomeric, or other terminal functionalgroup. Such terminal functionalization can be accomplished according toknown and established techniques. Examples of chemistry suitable forterminally functionalizing the polyolefin-polyradical of the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent are dehydrogenation, dehydration, hydrolysis, aminolysis,silylation, oxidation, oxidative esterification, and ion exchange (e.g.,to convert carboxylic acid groups to —CO₂Na moieties).

Referring to formula (IV), the terminal functional groups derived fromterminating the X portion(s) from formula (IV) at attachment(s) to M²are hydroxyl groups (i.e., —OH groups) when X is O; (C₁-C₂₀)hydrocarbylsubstituted amino groups (i.e., —NH—(C₁-C₂₀)hydrocarbyl) when X isN((C₁-C₂₀)hydrocarbyl); amino groups (—NH₂) when X is N(H); —SH groupswhen X is S; —PH₂ groups when X is P(H); and (C₁-C₂₀)hydrocarbylsubstituted phosphorous groups (i.e., —PH—(C₁-C₂₀)hydrocarbyl) when X isP((C₁-C₂₀)hydrocarbyl). Each of the terminal functional groups derivedfrom terminating the polyolefin-polyradical portion(s) from formula (IV)at attachment(s) to M¹ independently is the vinyl, hydroxyl, amine,silane, carboxylic acid, carboxylic acid ester, ionomeric, or otherterminal functional group. Preferably, the invention telechelicpolyolefin comprises a telechelic polyolefin of formula (V):T-polyolefin-CH₂—R^(L)—(X—H)_(w) (V), wherein w is an integer of 1 or 2;each R^(L) independently is (C₁-C₁₉)alkylene or (C₂-C₁₉)alkenylene; andeach X independently is as defined for formula (I). Accordingly,termination of the composition of formula (IV) produces a telechelicpolyolefin characterizable as having at least one terminal functionalgroup of formula —X—H and at least one terminal functional group offormula T-, wherein T is vinyl, hydroxyl, amine, silane, carboxylicacid, carboxylic acid ester, ionomeric, or other terminal functionalgroup, thereby establishing a preferred embodiment of the telechelicpolyolefin characterizable as having a non-statistical distribution ofterminal functional groups —X—H and T-.

In some embodiments, the invention process comprises a step ofterminating the polyolefin-polyradical of the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent to form the invention end functional polyolefin of formula (III).Again referring to formula (IV), terminally protonating thepolyolefin-polyradical followed by terminating the X portion(s) fromformula (IV) gives the invention end functional polyolefin of formula(III).

In the end functional polyolefin of formula (III) and the telechelicpolyolefin of formula (V), preferably w is 1.

In some embodiments, the polyolefin-polyradical of the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent is coupled through use of a polyfunctional coupling agent to forma new diblock, triblock- or higher block copolymer, which includeshyper-branched and dendrimers derivatives,

Preferably, the (polyolefin-polyradical)-containing multifunctionalchain shuttling agent is employed with a polyester-, polyether-,polyamide- or polyisocyanate-forming monomer in a respective inventionprocess for polymerizing the polyester-, polyether-, polyamide- orpolyisocyanate-forming monomer, thereby making the inventionpolyolefin/polyester, polyether-, polyamide-, or polyisocyanatemultiblock interpolymer (e.g., the invention poly(olefin monomer-olefincomonomer)/polyester, /polyether-, /polyamide-, or /polyisocyanatemultiblock interpolymer). Preferably, the polyester-, polyether-,polyamide- or polyisocyanate-forming monomer comprises ahydroxy-substituted carboxylic acid; a lactone; an oxetane; an oxirane(i.e., epoxide); a lactam; an isocyanate; a mixture comprising a dioland either a dicarboxylic acid, dicarboxylic diester, dicarboxylicanhydride, or dicarboxylic dihalide; or a mixture comprising adicarboxylic acid and an epoxide. In some embodiments, thepolyester-forming monomer comprises the lactone, the polyester-formingconditions comprise living anionic ring-opening polymerization, and thepolyolefin/polyester block copolymer comprises a polyolefin/ring-openedpolyester block copolymer. In some embodiments, the lactone comprisesε-caprolactone or (D,L)-lactide. In some embodiments, thepolyether-forming monomer comprises the epoxide (preferably ethyleneoxide or propylene oxide), the polyether-forming conditions compriseliving anionic ring-opening polymerization, and the polyolefin/polyetherblock copolymer comprises a polyolefin/ring-opened polyether blockcopolymer. In some embodiments, the polyamide-forming monomer comprisesthe lactam (preferably, 3-oxo-2-aziridinylidene, 1-methyl-2-azetidinone,N-methylbutyrolactam, N-methylvalerolactam, or N-methyl-6-caprolactam),the polyamide-forming conditions comprise living anionic ring-openingpolymerization, and the polyolefin/polyamide block copolymer comprises apolyolefin/ring-opened polyamide block copolymer. In some embodiments,the polyisocyanate-forming monomer comprises the isocyanate (preferably,phenylisocyanate, toluenediisocyanate or methylenediisocyanate), thepolyisocyanate-forming conditions comprise living anionicpolymerization, and the polyolefin/polyisocyanate block copolymercomprises a polyolefin polyisocyanate block copolymer.

The instant living anionic ring-opening polymerization step ofpolymerizing the polyester-, polyether-, or polyamide-forming monomer tomake the polyester, polyether, or polyamide portion of the inventionpolyolefin/polyester, polyolefin/polyether, or polyolefin/polyamidemultiblock interpolymer is an example of the aforementioned non-olefinpolymerization reaction.

The instant block interpolymers are comprised of two or more blocks orsegments which are joined to form a single interpolymer, and each blockor segment is chemically or physically distinguishable (other than bymolecular weight or molecular weight distribution) from adjoining blocksor segments, the resulting block interpolymer possesses unique physicaland chemical properties compared to random interpolymers of the samegross chemical composition. In some embodiments, the poly(olefinmonomer-olefin comonomer) comprise three or more blocks or segments and,thus, the poly(olefin monomer-olefin comonomer)/polyester, /polyether,/polyamide, and /polyisocyanate multiblock interpolymers comprise atotal of four or more blocks or segments per polymer molecule.Preferably, the poly(olefin monomer-olefin comonomer) portions thereofcomprise four or more blocks or segments and, thus, the respectiveinstant block respectively comprise a total of five or more blocks orsegments per polymer molecule.

In some embodiments, invention poly(olefin monomer-olefincomonomer)/polyester, poly(olefin monomer-olefin comonomer)/polyether,poly(olefin monomer-olefin comonomer)/polyamide, or poly(olefinmonomer-olefin comonomer)/polyisocyanate multiblock interpolymers arecharacterizable as having a high degree of polydispersity (e.g., PDIgreater than 3). In some embodiments, the poly(olefin monomer-olefincomonomer) portion thereof is characterizable as being derived from, andhaving the mesophase separation characteristics of, themesophase-separated olefin multiblock interpolymer.

In some aspects of the thirteenth embodiment, the process comprises astep of: contacting together ingredients comprising the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent comprising any one of the embodiments of the multifunctional chainshuttling agent (especially any one of the embodiments indirectlyincorporated later in claim 13 from any one of claims 1 to 8) andrespectively a polyester-, polyether-, polyamide-, orpolyisocyanate-forming monomer; the contacting step being performedunder polyester-, polyether-, polyamide-, or polyisocyanate-formingconditions, thereby respectively preparing a polyolefin/polyestermultiblock interpolymer, polyolefin/polyether multiblock interpolymer,polyolefin/polyamide multiblock interpolymer, orpolyolefin/polyisocyanate multiblock interpolymer.

The invention articles include objects comprising at least one filmlayer, such as a monolayer film, or at least one layer in a multilayerfilm prepared by cast, blown, calendered, or extrusion coatingprocesses; molded articles, such as blow molded, injection molded, orrotomolded articles; extrusions; fibers; and woven or non-woven fabrics.In some embodiments, the invention articles are comprised of or areformed from thermoplastic compositions comprising the inventive polymersincluding blends with other natural or synthetic polymers, additives,reinforcing agents, ignition resistant additives, antioxidants,stabilizers, colorants, extenders, crosslinking agents, blowing agents,and plasticizers.

Preferably, the article of the present invention comprises a natural or,preferably, synthetic lubricant. More preferably, the article of thepresent invention comprises an elastic film for a hygiene application(e.g., for a diaper cover); flexible molded good comprising anappliance, tool, consumer good (e.g., a toothbrush handle), sportinggood, building and construction component, automotive part, or medicalcomponent (e.g., device); flexible gasket (e.g., refrigerator doorgasket); flexible profile; an adhesive (e.g., for packaging, tape, orlabel); or a foam (e.g., for a sporting good, packaging, consumer good,automotive padding, or foam mat). Still more preferably, the article ofthe present invention comprises a photonic material, barrier film,separation membrane (also known as a microporous film), compatibilizer,or battery separator.

The term “photonic material” means a substance characterizable as havingperiodic, phase-separated mesodomains alternating in refractive index,with the domains sized to provide a photonic band gap in the UV-visiblespectrum, such as those disclosed in U.S. Pat. No. 6,433,931. Examplesof the photonic materials are a photonic crystal, photonic band gapmaterial, and elastomeric optical interference film. The photonicmaterials are useful in applications requiring reflectance,transmission, or both of electromagnetic radiation, especially ininfrared, visible, or ultraviolet wavelengths. Examples of suchapplications are anti-counterfeiting uses and security films,microtaggants, display films, and light filtering (e.g., backlitdisplays).

Examples of the barrier films are bladders in shoes (e.g., athleticshoes) and packaging (e.g., food packaging). Examples of the separationmembranes are membrane filters, including gas separation membranes,dialysis/hemodialysis membranes, reverse osmosis membranes,ultrafiltration membranes, and microporous membranes. Areas in whichthese types of membranes may be applicable include analyticalapplications, beverages, chemicals, electronics, environmentalapplications, and pharmaceuticals.

In addition, microporous polymeric films may be used as batteryseparators. Where the article comprises a battery separator, preferablyinstant block interpolymers comprising same is in a form of amicroporous polymeric film. Such microporous polymeric filmsadvantageously can be used as battery separators because of their easeof manufacture, chemical inertness and thermal properties. The principalrole of a battery separator is to allow ions to pass between theelectrodes but prevent the electrodes from contacting each other. Hence,the microporous polymeric films comprised of the instant blockinterpolymers preferably inhibit or prevent puncture thereof. Also, foruse in lithium-ion batteries the microporous polymeric films preferablywould shut-down (stop ionic conduction) at certain temperatures toprevent thermal runaway of the battery. Preferably, the instant blockinterpolymers used for the battery separator would have high strengthover a large temperature window to allow for either thinner or moreporous battery separators, or a combination thereof. Also, for lithiumion batteries lower shut-down temperatures are preferable, and themicroporous polymeric film preferably would maintain mechanicalintegrity after shut-down. Additionally, it is preferable that themicroporous polymeric film would maintain dimensional stability atelevated temperatures.

The microporous polymeric films of the present invention may be used inany of the processes or applications as described in, but not limitedto, the following patents and patent publications: WO2005/001956A2;WO2003/100954A2; U.S. Pat. No. 6,586,138; U.S. Pat. No. 6,524,742; US2006/0188786; US 2006/0177643; U.S. Pat. No. 6,749,961; U.S. Pat. No.6,372,379 and WO 2000/34384A1.

Preferably, the photonic material, barrier film, separation membrane,compatibilizer, or battery separator comprises, or is prepared from, themesophase-separated olefin multiblock interpolymer or the poly(olefinmonomer-olefin comonomer)/polyester, /polyether, /polyamide, or/polyisocyanate multiblock interpolymer having the portioncharacterizable as being derived from, and having the mesophaseseparation characteristics of, the mesophase-separated olefin multiblockinterpolymer. Suitable methods for manufacturing porous structures andmethods for forming patterns using block copolymer templates to formmesoporous materials are described in U.S. Pat. No. 7,517,466 B2. Foruse in or for preparing the photonic material or battery separator,preferably each of the mesophase-separated olefin multiblockinterpolymer or at least the mesophase-separated olefin multiblockinterpolymer portion of the poly(olefin monomer-olefincomonomer)/polyester, /polyether, /polyamide, or /polyisocyanatemultiblock interpolymer independently is characterizable as having atleast two domain sizes greater than 100 nm; a weight average molecularweight of less than 500,000 grams per mole; or more preferably both.

The mesophase separated structure provided by the instant blockinterpolymers provide several improvements over the prior art forforming microporous polymeric films. The ordered morphologies result ina greater degree of control over the pore size and channel structure.The phase separated melt morphology also limits film shrinkage in themelt and therefore imparts greater dimensional melt stability than innon-phase separated materials.

Materials and Methods

All solvents and reagents are obtained from commercial sources and usedas received unless indicated otherwise. Purify hexanes solvent through acolumn of activated alumina followed by a column of Q5 copper oxide onalumina (Cu-0226 S is obtained from (Engelhard, a subsidiary of BASFCorporation). Purify tetrahydrofuran (THF) and diethyl ether throughcolumns of activated alumina. Synthesize and store all metal complexesin a Vacuum Atmospheres inert atmosphere glove box under a dry nitrogenatmosphere. Record NMR spectra on a 300 megahertz (MHz) Varian INOVAspectrometer. Report chemical shifts in parts per million (δ) versustetramethylsilane and referenced to residual protons in a deuteratedsolvent.

Determine percent incorporation of 1-octene and polymer density byInfrared (IR) Spectroscopy: Deposit 140 microliters (μL) of each polymersolution in 1,2,4-trichlorobenzene (TCB) onto a silica wafer, heat at140° C. until the TCB evaporates, and analyze using a Nicolet Nexus 670FT-IR with 7.1 version software equipped with an AutoPro auto sampler.

Gel Permeation Chromatography (GPC):

Determine weight average molecular weight (M_(w)) and polydispersityindex: Determine M_(w) and ratio of M_(w)/M_(n) (polydispersity index orPDI) using a Polymer Labs™ 210 high temperature gel permeationchromatograph. Prepare samples using 13 mg of polyethylene polymer thatis diluted with 16 mL of 1,2,4-trichlorobenzene (stabilized withbutylated hydroxytoluene (BHT)), heat and shake at 160° C. for 2 hours.

Standard DSC method: Determine melting and crystallization temperaturesand heat of fusion by Differential Scanning calorimetry using a DSC 2910instrument (TA Instruments, Inc.): Under nitrogen purge gas, first heatsamples from room temperature to 180° C. at a heating rate of 10° C. perminute. Hold at this temperature for 2 to 4 minutes, cool the samples to−40° C. at a cooling rate of 10° C. per minute; hold the sample at thecold temperature for 2 to 4 minutes, and then heat the sample to 160° C.

Analyzing end groups by proton-nuclear magnetic resonance (¹H-NMR)spectroscopy using a Varian 600 MHz NMR instrument and deuteratedtetrachloroethane.

Abbreviations (meanings): r.t. and RT (room temperature); g (gram(s));mL (milliliter(s)); ° C. (degrees Celsius); mmol (millimole(s)); MHz(MegaHertz); Hz (Hertz).

EXAMPLE(S) OF THE PRESENT INVENTION

The following examples are provided to further illustrate, but not limitscope of, the present invention.

Example 1 Synthesis of Multifunctional (Dual Functional) Chain ShuttlingAgent (1)

Set up and run the reaction in a nitrogen-purged glovebox. Weightriisobutylaluminum (3.4 g, 17 mmol) into a glass jar charged with apolytetrafluoroethylene (PTFE)-coated stir bar and dissolve in 20 mL ofhexanes. Weigh 5-hexen-1-ol (2.0 mL, 17 mmol) into a small glass vialand dissolve in 5 mL of hexanes. Place both solutions in a freezer at−40° C. Remove the solutions and add half of the 5-hexen-1-ol solutiondropwise to the triisobutylaluminum solution while stirring. Afteradding about half of the 5-hexen-1-ol solution, place the solutions backin the freezer to cool back to −40° C. Remove the solutions after about10 minutes and add the remainder of the 5-hexen-1-ol solution dropwiseto the stirring reaction solution. Stir the resulting combined solutionfor 2 hours at room temperature (RT). Place the combined solution undervacuum to remove solvent. Analyze the resulting intermediate (3.68 g, 15mmol) by ¹H-NMR and ¹³C-NMR spectroscopy (C₆D₆). Dissolve theintermediate in 10 mL of toluene. Add to the resulting toluene mixturediisobutylaluminum hydride (2.18 g, 15.3 mmol). Stir the resultingmixture overnight at 50° C. in an aluminum heating block. Place theresulting colorless solution under vacuum to remove toluene. Theresulting viscous liquid product is not soluble in d6-benzene (C₆D₆).Take a ¹H-NMR spectrum in d8-THF: observe olefin peaks in the spectrum;approximately 17 weight % of the sample is the olefin as estimated byNMR. Transfer a majority of the product (4.23 g) to another glass jarand dissolve it in toluene (10 mL). Add diisobutylaluminum hydride (0.47g). Stir the resulting solution with a PTFE-coated stir bar overnight at50° C. Remove solvent in vacuo and transfer the resulting final productto a separate jar. Analyze the final product by NMR in d8-THF; the NMRspectrum is consistent with (1).

Example 2 Synthesis of Multifunctional Chain Shuttling Agent (2)

Set up and run the reaction in a nitrogen-purged glovebox. Weightriisobutylaluminum (3.47 g) into a glass jar charged with a PTFE-coatedstir bar and dissolve in toluene (20 mL). Weigh allyl alcohol (1.0 g)into a small glass vial and dissolve in toluene (10 mL). Seal bothsolutions with PTFE-lined caps and place them in a freezer at −40° C.for 10 minutes. Remove the solutions from the freezer and slowly add thealcohol solution to the aluminum solution while stirring. After abouthalf the alcohol solution is added, recool the solutions to −40° C. inthe freezer. Remove the solutions from the freezer and slowly add theremainder of the alcohol. Stir the mixture at room temperature (RT) forabout 2 hours. Place the solution under vacuum to remove solvent andyield a colorless liquid (3.18 g, FW 182.28). Take a proton NMR spectrumof the liquid in d-benzene: the spectrum indicates the desiredintermediate is present. Add one mole equivalent (relative to theisolated product) of diisobutylaluminum hydride to the liquid. Stir andheat the resulting solution to 60° C. in an aluminum heating block andstir for a total of 8 hours. ¹H NMR spectra shows the reaction is notcomplete after 4 hours and 8 hours. Stir the solution overnight at 75°C. while only lightly capped (to allow for loss of isobutylene). Placethe liquid under vacuum: a small amount of gas comes out of solution,potentially due to a loss of isobutylene. Take NMR spectra of theremaining liquid: very messy spectra, consistent with the formation ofmultiple bridging species, but most of the vinyl group has beenconverted. Transfer the liquid to a vial: 3.48 g. Transfer a sample ofthe liquid to a small vial and dissolve in deuterated methylenechloride. Add deuterated methanol: observe a vigorous reaction andsignificant white solid forms. Stir the solution for over 1 hour. Dilutethe solution with more deuterated methylene chloride and filter througha 0.45 micron disposable PTFE syringe frit. Take ¹H and ¹³C NMR spectra:spectra are consistent with the presence of CH₂DCH₂CH₂OD andCH₂D-CH(CH₃)₂. This result is consistent with the liquid containing (2).

Example 3 Polymerization of 1-octene with Multifunctional ChainShuttling Agent (1) to Give (Polyolefin-polyradical)-ContainingMultifunctional Chain Shuttling Agent (3)

Set up and run the reaction in a nitrogen-purged glovebox. Weigh themultifunctional chain shuttling agent (1) of Example 1 (0.31 g) into aglass jar charged with a PTFE-coated stir bar and add 1-octene (22.4 g).The multifunctional chain shuttling agent (1) becomes a white solid inthe 1-octene. Add toluene (40 mL). Heat the resulting mixture to 45° C.to dissolve most of the multifunctional chain shuttling agent (1). Forma catalyst solution by combining a solution of Catalyst (A1) as shownearlier (0.20 mL of a 0.005 M solution of in toluene) and a solution ofcocatalyst (cocatalyst=bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borate ([HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄],abbreviated as BOMATPB) (0.22 mL of a 0.005 M solution) about 5 minutesprior to their addition to the polymerization reaction. Add the catalystsolution to the polymerization reaction to give a reaction mixture.Place a thermocouple in the reaction mixture to monitor the temperature.The temperature rises to about 58° C. in 30 minutes before stabilizing.The solution becomes viscous. Once the temperature stops increasing,remove the reaction mixture from the aluminum heating block and placedin a freezer and −40° C. Remove solvent from the reaction mixture invacuo and keep the resulting reaction product comprising (3) undervacuum overnight at 60° C. Take ¹H and ¹³C NMR spectra of a sample ofthe reaction product in d8-toluene: observe the spectra are consistentwith (3).

Example 4 Polymerization of D,L-lactide with Multifunctional ChainShuttling Agent (1)

Day 1. In a N₂ glove box, add 5 mL of toluene to 20 mL vial charged witha stir bar and 0.249 g of initiator, the initiator being themultifunctional chain shuttling agent (1) of Example 1. The initiatordoes not completely dissolve at room temperature. Add 2.38 g ofD,L-lactide to the vial followed by an additional 11 mL of toluene. Capthe reaction mixture and heat it to 70° C. using a thermocouple,heat-controlled glove box. (Turn heat on at 10:30 am and temperaturereaches 70° C. at 10:40 am). Stir reaction overnight at 70° C.Day 2. At 8 a.m., observe the reaction mixture has stopped stirring.Remove the vial cap and replace with a septum. Remove the vial from theglove box and quench it with about 0.3 mL of a 1 M HCl solution. Take anNMR spectrum of a sample in CDCl₃. Transfer the reaction mixture to aflask containing about 50 mL of methanol. Cool the cloudy mixture usinga dry ice/acetone bath. Scoop out the resulting viscous polymer from thecloudy solution and place it into a small vial. Blow N₂ gas over thesample overnight to remove solvent to give final polymer product.Day 3 Take a ¹H NMR spectrum of the final polymer product in CDCl₃. Thespectrum is consistent with the final polymer product comprising poly(D,L-lactide).

Example 5 Preparation of Poly(octene-(D,L)-lactide) Diblock Copolymer

Repeat the procedure of Example 4 except instead of using themultifunctional chain shuttling agent (1) use instead the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent (3) to give poly(octene-(D,L)-lactide) diblock copolymer. Thepoly(octene-(D,L)-lactide) diblock copolymer is characterized as havinga polyoctene block and a poly((D,L)-lactide) block, and an oxygenlinking the polyoctene block to the poly((D,L)-lactide) block.

Example 6a Preparation of a Telechelic Polyoctene

Contact the (polyolefin-polyradical)-containing multifunctional chainshuttling agent (3) to dehydrogenation conditions (e.g., displacement ofR₂Al with excess of an alpha-olefin such as isobutylene in Isopar E),followed by acidification to give the telechelic polyoctene (4), whichis drawn to illustrate vinyl and hydroxyl terminal functional groups.

Example 6b Preparation of a Telechelic Polyoctene

Contact a suspension of the (polyolefin-polyradical)-containingmultifunctional chain shuttling agent (3) in toluene with a stream ofoxygen for 1.5 hours at 60° C. (see Burfield, Polymer 1984; 25:1817-1822for precedent). After the reaction is complete, quench the reaction bythe addition of HCl in methanol to give the telechelic polyoctene (4).

Example 7 Synthesis of Multifunctional Chain Shuttling Agent (5)

Repeat the procedure of Example 1 except as noted here. Use toluene (30mL) to dissolve triisobutylaluminum (10.9 g) instead of hexanes;2,7-octadien-1-ol (8.0 mL) instead of the 5-hexen-1-ol; toluene (10 mL)to dissolve the 2,7-octadien-1-ol instead of the hexanes; to giveintermediate diisobutylaluminum 2,7-octadien-1-oxide (14.3 g), andanalyze the intermediate by ¹H-NMR spectroscopy (C₆D₆). (Note gasvigorously evolves during addition of the 2,7-octadien-1-ol solution intoluene to the triisobutylaluminum solution in toluene.) Add neatdiisobutylaluminum hydride (3.8 g, 1.05 mole equivalents) to a portion(6.76 g) of the intermediate, and heat the resulting mixture at 60° C.for 6 hours. ¹H-NMR spectroscopy (d8-THF) shows incomplete conversion ofterminal olefin functional group. Add additional neat diisobutylaluminumhydride (0.4 mL) and stir at 60° C. overnight. Add hexane to give acolorless solution. Remove hexane under vacuum to give a colorless oil.Remove a 1.1 g portion and set aside remainder. Determine solubility ofthe resulting colorless oil: add 5 mL hexane to a 1.1 g portion of thecolorless oil; mix; isolate a bottoms gel of 0.3 g solid; remainder of1.1 g portion remains dissolved in hexane. Place remainder of colorlessoil in 150 mL glass jar, and add 1-octene (5 mL) to it to consume excessaluminum hydride species. Seal jar, stir in aluminum heating block at75° C. for 3 hours, then at room temperature overnight. Remove residual1-octene in vacuo over 24 hours to give the multifunctional chainshuttling agent (5) as a colorless oil (6.1 g); ¹H-NMR spectroscopy(d8-THF) is consistent with (5).

Example 8 Polymerization of 1-octene with Multifunctional ChainShuttling Agent (5) to Give (Polyolefin-polyradical)-ContainingMultifunctional Chain Shuttling Agent (6)

Repeat the procedure of Example 3 except use the multifunctional chainshuttling agent (5) of Example 7 instead of multifunctional chainshuttling agent (1) to give the (polyolefin-polyradical)-containingmultifunctional chain shuttling agent (6).

Example 9 Synthesis of Multifunctional Chain Shuttling Agent (5a)

In a procedure similar to that of Example 7, a reaction is set up andrun in a nitrogen purged glovebox. Weigh intermediate diisobutylaluminum2,7-octadien-1-oxide (10.0 g, 37.5 mmol, prepared as in Example 7) intoa glass jar charged with a poly(tetrafluoroethylene) (PTFE)-coated stirbar. Add to this diisobutylaluminum hydride (5.4 g, 37.5 mmol) at roomtemperature (RT) while stirring. Seal the glass jar, and stir theresulting mixture for 6 hours at 60° C. ¹H NMR spectroscopy of thestirred mixture shows that a significant amount of unreacted vinylgroups are still present. Add another 80 mg of diisobutylaluminumhydride, and stir the new mixture overnight at 50° C. Add 1-octene (20mL) to the new stirred mixture, and stir the resulting solution for 4hours at 100° C. with a reflux condenser over the solution. Removevolatiles in vacuo, and analyze the residual product by ¹H NMRspectroscopy (d8-THF). The ¹H NMR data are consistent withmultifunctional chain shuttling agent (5a), and show that approximatelyone isobutyl-Al group per aluminum in the intermediatediisobutylaluminum 2,7-octadien-1-oxide is converted to an n-octyl-Algroup as shown in (5a).

Example 10 Polymerization of 1-octene with Multifunctional ChainShuttling Agent (5a) to Give (Polyoctene-polyradical)-ContainingMultifunctional Chain Shuttling Agent (6a)

A reaction is set up and run in a nitrogen purged glovebox. Weighmultifunctional chain shuttling agent (5a) (1.5 g, about 3.0 mmol,Example 9) into a 120 mL glass jar with a PTFE-coated stir bar. Adddiethylzinc (0.10 g, 0.75 mmol), and dilute the resulting mixture with25 mL toluene. Add 1-octene (3 mL, 19 mmol) to the resulting solutionwith stirring. Place the stirring solution in an external (to the glassjar) aluminum heating block set at 60° C. and monitor the internaltemperature of the solution with a thermocouple probe. Separately,combine Catalyst (A1) (0.3 mL of a 0.005M solution in toluene) withBOMATPB (0.36 mL of a 0.005M solution in toluene) in a small glass vial.Add the resulting contents of the vial to the solution to give areaction solution. Add additional 1-octene to the reaction solution at arate of 3 mL thereof every 10 minutes. After 30 minutes, no significantexotherm is noted, so make two separate additions of new solutions ofCatalyst (A1) and BOMATPB (prepared as before) to the reaction solution.(Total catalyst amounts added overall: 4.5 μmol Catalyst (A1) and 5.4μmol BOMATPB.) Temperature of the resulting reaction solution rises to67° C. Maintain the temperature below 67° C. by lowering temperature ofthe external aluminum heating block. Add additional 1-octene at a rateof about 3 mL every 10 minutes until an overall total of 27 mL (173mmol) of 1-octene is added. This prepares(polyoctene-polyradical)-containing multifunctional chain shuttlingagent (6a) in situ. Quench the reaction by the addition of methanolthereto. Stir the resulting methanol-containing mixture for 4 hours at60° C. to fully quench any alkylaluminum compounds. Remove solvent(toluene, methanol, excess 1-octene) in vacuo, and dry the resultingresidue overnight at 60° C. under vacuum to yield 11.8 g of initialbatch (polyoctene-polyradical)-containing multifunctional chainshuttling agent (6a). Analyze molecular weight of initial batch (6a) ona Viscotek gel permeation chromatography (GPC) instrument: M_(n) is2,446 g/mol and PDI is 3.63. From the molecular weight data, it isconcluded that both Al and Zn are chain transferring in the abovereaction with the catalyst (prepared from Catalyst (A1) and BOMATPB, asnative M_(n) of polyoctene is greater than 141,000 g/mol under samereaction conditions except lacking multifunctional chain shuttling agent(5a) and diethyl zinc.

Solvent treatment of initial batch (6a). Dissolve initial batch (6a) ina small amount of toluene and add 60 mL methanol. Stir the resultingmixture for 2 hours at 60° C. Pour off the resulting liquid from solids,and wash the solids with hot methanol. Dry the washed solids overnightat 100° C. under vacuum to give solvent treated (6a). Analyze solventtreated (6a) by ¹H NMR spectroscopy (CDCl₃). Terminal alkoxy-Al group ispresent at 4.1 ppm and is present at a ratio of 1 terminal alkoxy-Algroup per 274 octylene monomer units (determined from integration of CH₃side chains). Analyze solvent treated (6a) by Viscotek GPC as before.Determine M_(n) is 5,060 g/mol and PDI is 1.86 for solvent treated (6a).Molecular weight distribution of solvent treated (6a) shows a sharpcutoff below about 1000 (10³) Daltons. Lower molecular weight polymercomponents in initial batch (6a) appear to have been removed by thesolvent treatment. From the ¹H-NMR spectrum and the molecular weightdata, it can be estimated that 16 mol % of the polymer chains in solventtreated (6a) are terminated by an alkoxy-Al group.

As shown by the Examples, the invention multifunctional chain shuttlingagents are characterizable as having at least two mutually compatible,yet different functional activities. One of the functional activitiescomprises a chain shuttling function. Another of the functionalactivities comprises a protecting/polymerization initiating function,which comprises a protecting group function or, in some embodiments, apolymerization initiating function, or in some embodiments both. Themultifunctional chain shuttling agents incorporate at least twometal-containing, differently functional moieties into a single compoundor molecule. The metal-containing functional moiety employed for chainshuttling successfully carries out chain shuttling functional activityin the presence of the metal-containing functional group employed forpolymerization initiation or group protection. The invention providesfor terminally functionalizing the polyolefin-polyradical of the(polyolefin-polyradical)-containing multifunctional chain shuttlingagent or a means for initiating polymerization functional activity inthe presence of the metal-containing functional group employed for chainshuttling. Such mutual compatibility between what until now could havebeen considered potentially conflicting functional moieties andactivities is particularly valuable for making amphiphilic diblock andmultiblock copolymers, especially in a continuous polymerizationprocess.

While the present invention has been described above according to itspreferred aspects or embodiments, it can be modified within the spiritand scope of this disclosure. This application is therefore intended tocover any variations, uses, or adaptations of the present inventionusing the general principles disclosed herein. Further, the applicationis intended to cover such departures from the present disclosure as comewithin the known or customary practice in the art to which this presentinvention pertains and which fall within the limits of the followingclaims.

What is claimed is:
 1. A process for preparing a multifunctionalcomposition, the process comprising a step of: contacting togetheringredients comprising: a multifunctional chain shuttling agentcomprising a compound having one or more moieties capable of chainshuttling, one or more moieties capable of protecting or polymerizationinitiating, and at least one polyvalent linking group; the chainshuttling moieties being different than the protecting/polymerizationinitiating moieties, each chain shuttling moiety and polymerizationinitiating moiety independently comprising a metal cation, each metal ofthe metal cations independently being tin or a metal of any one ofGroups 2, 12, and 13 of the Periodic Table of the Elements; eachpolyvalent linking group independently comprising from 2 to 20 carbonatoms; 0, 1, or 2 carbon-carbon double bonds; and from 1 to 4heteroatoms, each heteroatom independently being either an oxygen atom,sulfur atom, hydrogen-substituted nitrogen atom, hydrocarbyl-substitutednitrogen atom, hydrogen-substituted phosphorous atom, orhydrocarbyl-substituted phosphorous atom; each metal cation of a chainshuttling moiety independently being bonded to a different carbon atomof the same polyvalent linking group or to a carbon atom of a differentpolyvalent linking group and each metal cation of a polymerizationinitiating moiety independently being bonded to a different heteroatomof the same polyvalent linking group or to a heteroatom of a differentpolyvalent linking group, the metal cations thereby being spaced apartfrom each other by at least one polyvalent linking group; an originalolefin polymerization catalyst; and, an original cocatalyst, thecontacting being performed under catalyst preparing conditions, therebypreparing the multifunctional composition, the multifunctionalcomposition being capable of functioning as a multifunctional chainshuttling agent and an olefin polymerization catalyst.
 2. Amultifunctional composition comprising the multifunctional compositionprepared by the process as in claim
 1. 3. A process for preparing amultifunctional composition, the process comprising a step of:contacting together ingredients comprising: a multifunctional chainshuttling agent comprising a single compound that is characterized asbeing capable of functioning in such a way that at least oneolefin-containing polymeryl chain is capable of being shuttled betweentwo or more catalytic sites of an olefin polymerization catalyst havingtwo or more catalytic sites or between two or more olefin polymerizationcatalysts; and, independently either: (a) a non-olefin polymerizationreaction is capable of being initiated by the multifunctional chainshuttling agent; (b) a functional group of the multifunctional chainshuttling agent is capable of being characterized as being protectedwith a protecting group during the chain shuttling, and thenincorporated into the olefin-containing polymeryl chain; or (c) anon-olefin polymerization reaction is capable of being initiated by thefunctional group after it has been incorporated into theolefin-containing polymeryl chain; an original olefin polymerizationcatalyst; and, an original cocatalyst, the contacting being performedunder catalyst preparing conditions, thereby preparing themultifunctional composition, the multifunctional composition beingcapable of functioning as a multifunctional chain shuttling agent and anolefin polymerization catalyst.
 4. A multifunctional compositioncomprising the multifunctional composition prepared by the process as inclaim 3.